Pesticidally active heterocyclic derivatives with sulfoximine containing substituents

ABSTRACT

Compounds of the formula (I), wherein the substituents are as defined in claim  1 . Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling animal pests, including arthropods and in particular insects, nematodes, molluscs or representatives of the order Acarina.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a 371 National Stage application of InternationalApplication No. PCT/EP2019/064795 filed Jun. 6, 2019 which claimspriority to IN 201811021198, filed Jun. 6, 2018, and EP 18191693.3,filed Aug. 30, 2018, the entire contents of these applications arehereby incorporated by reference.

The present invention relates to pesticidally active, in particularinsecticidally active heterocyclic derivatives containing sulfoximinesubstituents, to processes for their preparation, to compositionscomprising those compounds, and to their use for controlling animalpests, including arthropods and in particular insects or representativesof the order Acarina.

Pesticidally active hetero-bicyclic substituted cyclopropyl derivativeswith sulfur-containing substitutents are known and described in theliterature, for example, in WO 2018/077565, WO 2018/070502, WO2017/146226, WO 2017/089190, WO 2017/084879, WO 2016/121997, WO2016/104746, WO 2016/096584, WO 2016/046071, WO 2016/071214, WO2016/039441, WO 2016/026848, WO 2016/023954, WO 2014/142292, and WO2016/020286. Pesticidally active heterocyclic sulfoximine derivativeshave previously been described in the literature, for example, in WO2015/071180.

It has now surprisingly been found that certain novel bicyclicsulfoximine-containing substituted cyclopropyl derivatives havefavorable properties as pesticides.

The present invention therefore provides compounds of formula I,

wherein

A is CH or N

R₁ is C₁-C₄ alkyl

R₂ is hydrogen, cyano, —C(O)R₇, —C(O)OR₈, C₁-C₆alkyl or —CONR₉R₁₀,SO₂R₁₁

wherein

R₇ is hydrogen, C₁-C₆alkyl or C₁-C₆haloalkyl and R₃ is C₁-C₆alkyl orC₁-C₆haloalkyl;

R₉, R₁₀ independently of one another are hydrogen or C₁-C₆alkyl;

R₁₁ is C₁-C₆alkyl;

R₃ is hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano, —CO₂H, —CO₂NH₂,C₁-C₄alkoxycarbonyl, C₁-C₄alkylaminocarbonyl, C₁-C₄dialkylaminocarbonyl

n is 0 or 1;

Q is a radical selected from the group consisting of formulae Q₁, Q₂,Q₃, Q₄ and Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein

R₄ is halogen, C₁-C₆haloalkyl, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl or C₁-C₆haloalkoxy;

X₁ is O or NR₅;

R₅ is C₁-C₄alkyl;

R₆ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, or C₃-C₆cycloalkyl;

G₁ and G₂ are, independently from each other, N or CH;

or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomeror N-oxide of a compound of formula I.

Compounds of formula I which have at least one basic centre can form,for example, acid addition salts, for example with strong inorganicacids such as mineral acids, for example perchloric acid, sulfuric acid,nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, withstrong organic carboxylic acids, such as C₁-C₄alkanecarboxylic acidswhich are unsubstituted or substituted, for example by halogen, forexample acetic acid, such as saturated or unsaturated dicarboxylicacids, for example oxalic acid, malonic acid, succinic acid, maleicacid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids,for example ascorbic acid, lactic acid, malic acid, tartaric acid orcitric acid, or such as benzoic acid, or with organic sulfonic acids,such as C₁-C₄alkane- or arylsulfonic acids which are unsubstituted orsubstituted, for example by halogen, for example methane- orp-toluenesulfonic acid. Compounds of formula I which have at least oneacidic group can form, for example, salts with bases, for examplemineral salts such as alkali metal or alkaline earth metal salts, forexample sodium, potassium or magnesium salts, or salts with ammonia oran organic amine, such as morpholine, piperidine, pyrrolidine, a mono-,di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- ordimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, forexample mono-, di- or triethanolamine.

The term “C₁-C_(n)alkyl” as used herein refers to a saturatedstraight-chain or branched hydrocarbon radical attached via any of thecarbon atoms having 1 to n carbon atoms, for example, any one of theradicals methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,iso-butyl, tert-butyl, pentyl, hexyl, and their branched isomers. Forexample, there also may be mentioned any one of the radicals1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl,1-ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl,1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl,4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl. As noted below,haloalkyl, haloalkylsulfanyl, haloalkylsulfinyl, haloalkylsulfonyl,alkoxy and haloalkoxy radicals are derived from the alkyl radicals.

Halogen is generally fluorine, chlorine, bromine or iodine. This alsoapplies, correspondingly, to halogen in combination with other meanings,such as haloalkyl.

The term “C₁-C_(n)haloalkyl” as used herein refers to a straight-chainor branched saturated C₁-C_(n)alkyl radical having 1 to n carbon atoms(as mentioned above), where some or all of the hydrogen atoms in theseradicals may be replaced by fluorine, chlorine, bromine and/or iodine,i.e., for example, for example, any one of chloromethyl, dichloromethyl,trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl,2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl,2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl,2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl,2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl,3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl,1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl,1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl,4-bromobutyl, nonafluorobutyl 1,1-difluoro-2,2,2-trichloroethyl, and2,2,3,3-tetrafluoroethyl; preferably trichloromethyl,difluorochloromethyl, difluoromethyl, trifluoromethyl anddichlorofluoromethyl.

The term “C₁-C_(n)alkoxy” as used herein refers to a straight-chain orbranched saturated C₁-C_(n)alkyl radical having 1 to n carbon atoms (asmentioned above) which is attached via an oxygen atom, i.e., forexample, any one of the radicals methoxy, ethoxy, propoxy, i-propoxy,n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, 1-methylpropoxy,2-methylpropoxy and 1,1-dimethylethoxy and also the isomeric pentyloxyand hexyloxy radicals; preferably methoxy and ethoxy.

The term “C₁-C_(n)haloalkoxy” as used herein refers to a straight-chainor branched saturated C₁-C_(n)haloalkyl radical having 1 to n carbonatoms (as mentioned above) which is attached via an oxygen atom similarto C₁-C_(n)alkoxy.

The term “C₁-C_(n)alkylsulfanyl” as used herein refers to a straightchain or branched saturated alkyl radical having 1 to n carbon atoms (asmentioned above) which is attached via a sulfur atom, i.e., for example,any one of methylthio, ethylthio, n-propylthio, 1-methylethylthio,butylthio, 1-methylpropylthio, 2-methylpropylthio or1,1-dimethylethylthio.

The term “C₁-C_(n)haloalkylsulfanyl” as used herein refers to aC₁-C_(n)alkylsulfanyl radical as mentioned above which is partially orfully substituted by fluorine, chlorine, bromine and/or iodine, i.e.,for example, any one of fluoromethylthio, difluoromethylthio,trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio,2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio,2,2-difluoroethylthio, 2,2,2-trifluoroethylthio,2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio,2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio,pentafluoroethylthio, 2-fluoropropylthio, 3-fluoropropylthio,2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio,3-bromopropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio,2,3-dichloropropylthio, 3,3,3-trifluoropropylthio,3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio,heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio,1-(chloromethyl)-2-chloroethylthio, 1-(bromomethyl)-2-bromoethylthio,4-fluorobutylthio, 4-chlorobutylthio, or 4-bromobutylthio.

Similar considerations apply to the terms “C₁-C_(n)haloalkylsulfinyl”and “C₁-C_(n)haloalkylsulfonyl” which refer to theC₁-C_(n)haloalkylsulfanyl (as mentioned above), but with the sulfur in adifferent oxidation state, for example, sulfoxide —S(O)C₁-C_(n)haloalkylor sulfone —S(O)₂C₁-C_(n)haloalkyl, respectively.

Accordingly, for example, groups such as trifluoromethylsulfinyl,trifluoromethylsulfonyl or 2,2,2-trifluoroethylsulfonyl.

The term “C₃-C₆cycloalkyl” as used herein refers to 3-6 memberedcycloalkyl groups such as cyclopropane, cyclobutane, cyclopropane,cyclopentane and cyclohexane.

The term “C₁-C_(n)alkoxycarbonyl” refers to a straight-chain or branchedsaturated C₁-C_(n)alkoxy radical having 1 to n carbon atoms (asmentioned above) which is attached via a carbonyl group.

The term “C₁-C_(n)alkylaminocarbonyl” refers to a straight-chain orbranched saturated C₁-C_(n)alkyl radical having 1 to n carbon atoms (asmentioned above) which is attached via the nitrogen atom of anaminocarbonyl group.

The term “C₁-C_(n) dialkylaminocarbonyl” refers to two straight-chain orbranched saturated C₁-C_(n)alkyl radicals having 1 to n carbon atoms (asmentioned above), the same or different, which are attached via thenitrogen atom of an aminocarbonyl group

Terminal single bonds (Free radicals) represent methyl groups within thecontext of a given molecular structure or represent a point ofattachment in the context of a variable group definition.

The compounds of formula I according to the invention also includehydrates which may be formed during the salt formation.

Embodiments according to the invention are provided as set out below.

Embodiment 1 provides compounds of formula I, or an agrochemicallyacceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof,as defined above.

Embodiment 2 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiment 1 wherein:

A is CH or N;

R₁ is ethyl, propyl or isopropyl;

R₂ is hydrogen, cyano, C₁-C₃ alkyl, C₁-C₃alkylcarbonyl,C₁-C₃alkoxycarbonyl, C₁-C₃haloalkylcarbonyl;

R₃ is hydrogen, C₁-C₃haloalkyl, cyano, —CO₂H, —CO₂NH₂,C₁-C₄dialkylaminocarbonyl; and n is 1.

Embodiment 3 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiment 1 wherein:

A is CH or N;

R₁ is ethyl;

R₂ is hydrogen;

R₃ is hydrogen, C₁-C₂haloalkyl, cyano, —CO₂NH₂,C₁-C₂dialkylaminocarbonyl; and n is 1.

Embodiment 4 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiment 1 wherein:

A is CH or N;

R₁ is ethyl;

R₂ is hydrogen;

R₃ is hydrogen, cyano or CO₂NH₂; and n is 1.

Embodiment 5 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiment 1 wherein:

A is CH or N;

R₁ is ethyl;

R₂ is hydrogen;

R₃ is hydrogen or cyano; and n is 1.

Embodiment 6 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiment 1 wherein:

Q is a radical selected from Q₁, Q₂, Q₄ and Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein

R₄ is C₁-C₂haloalkyl, C₁-C₂haloalkylsulfanyl, C₁-C₂haloalkylsulfinyl orC₁-C₂haloalkylsulfonyl;

X₁ is oxygen or NCH₃;

R₆ is C₁-C₂alkyl, C₁-C₂haloalkyl, C₁-C₂alkoxy or cyclopropyl; and

G₁ and G₂ are, independently from each other, N or CH.

Embodiment 7 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiment 1 wherein:

is a radical selected from Q₁, Q₂ and Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein

R₄ is C₁-C₂fluoroalkyl, trifluoromethylsulfanyl,trifluoromethylsulfinyl, trifluoromethylsulfonyl,difluoromethylsulfanyl, difluoromethylsulfinyl, ordifluoromethylsulfonyl;

X₁ is NCH₃;

R₆ is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and

G₁ and G₂ are, independently from each other, N or CH.

Embodiment 8 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiment 1 wherein:

Q is a radical selected from Q₁ and Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein

R₄ is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl,trifluoromethylsulfinyl or trifluoromethylsulfonyl;

X₁ is NCH₃;

R₆ is ethyl, methoxy or cyclopropyl; and

G₁ is N and G₂ is CH, or G₁ is CH and G₂ is N, or G₁ and G₂ are N, or G₁and G₂ are CH.

Embodiment 9 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiment 1 wherein:

Q is radical Q₁

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein

R₄ is trifluoromethyl;

X₁ is NCH₃; and

G₁ is N and G₂ is CH, G₁ is CH and G₂ is N, or G₁ and G₂ are N.

Embodiment 10 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiment 1 wherein:

A is CH or N;

R₁ is ethyl, propyl or isopropyl;

R₂ is hydrogen, cyano, C₁-C₃ alkyl, C₁-C₃alkylcarbonyl,C₁-C₃alkoxycarbonyl, C₁-C₃haloalkylcarbonyl;

R₃ is hydrogen, C₁-C₃haloalkyl, cyano, CO₂H, CO₂NH₂,C₁-C₄dialkylaminocarbonyl;

n is 1;

Q is a radical selected from Q₁, Q₂, Q₄ and Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein

R₄ is C₁-C₂haloalkyl, C₁-C₂haloalkylsulfanyl, C₁-C₂haloalkylsulfinyl orC₁-C₂haloalkylsulfonyl;

X₁ is oxygen or NCH₃;

R₆ is C₁-C₂alkyl, C₁-C₂haloalkyl, C₁-C₂alkoxy or cyclopropyl; and

G₁ and G₂ are, independently from each other, N or CH.

Embodiment 11 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiment 1 wherein:

A is CH or N;

R₁ is ethyl;

R₂ is hydrogen;

R₃ is hydrogen, C₁-C₂haloalkyl, cyano, CO₂NH₂,C₁-C₂dialkylaminocarbonyl;

n is 1;

Q is a radical selected from Q₁, Q₂ and Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein

R₄ is C₁-C₂fluoroalkyl, trifluoromethylsulfanyl,trifluoromethylsulfinyl, trifluoromethylsulfonyl,difluoromethylsulfanyl, difluoromethylsulfinyl, ordifluoromethylsulfonyl;

X₁ is NCH₃;

R₆ is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and

G₁ and G₂ are, independently from each other, N or CH.

Embodiment 12 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiment 1 wherein:

A is CH or N;

R₁ is ethyl;

R₂ is hydrogen;

R₃ is hydrogen, cyano or CO₂NH₂;

n is 1;

Q is a radical selected from Q₁ and Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein

R₄ is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl,trifluoromethylsulfinyl or trifluoromethylsulfonyl;

X₁ is NCH₃;

R₆ is ethyl, methoxy or cyclopropyl; and

G₁ is N and G₂ is CH, or G₁ is CH and G₂ is N, or G₁ and G₂ are N, or G₁and G₂ are CH.

Embodiment 13 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiment 1 wherein:

A is CH or N;

R₁ is ethyl;

R₂ is hydrogen;

R₃ is hydrogen or cyano;

n is 1;

Q is radical Q₁

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein

R₄ is trifluoromethyl;

X₁ is NCH₃; and

G₁ is N and G₂ is CH, G₁ is CH and G₂ is N, or G₁ and G₂ are N.

Embodiment 14 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiments 1, 2, 3, 4 or 5 wherein:

Q is a radical selected from Q₁₋₁, Q₁₋₂, Q₁₋₃, Q₁₋₄ and Q₁₋₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and

R₄ is trifluoromethyl, trifluoromethylsulfanyl ortrifluoromethylsulfonyl.

Embodiment 15 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiment 14:

wherein Q is a radical selected from Q₁₋₂, Q₁₋₃, Q₁₋₄ and Q₁₋₅.

Embodiment 16 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiments 1, 2, 3, 4 or 5 wherein:

Q is a radical selected from Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A;

R₄ is trifluoromethyl, trifluoromethylsulfanyl ortrifluoromethylsulfonyl; and

R₆ is OCH₃, CH₂CH₃ or cyclopropyl.

Embodiment 17 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiments 1, 2, 3, 4 or 5 wherein:

Q is a radical Q₂

wherein the arrow denotes the point of attachment to the ringincorporating the radical A;

R₄ is trifluoromethyl, trifluoromethylsulfanyl ortrifluoromethylsulfonyl; and

G₂ is N or CH.

Embodiment 18 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiments 1, 2, 3, 4 or 5 wherein:

Q is Q₃; and

R₄ is trifluoromethyl, trifluoromethylsulfanyl ortrifluoromethylsulfonyl.

Embodiment 19 provides compounds, or an agrochemically acceptable salt,stereoisomer, enantiomer, tautomer or N-oxide thereof, according toembodiments 1, 2, 3, 4 or 5 wherein:

Q is Q₄

wherein the arrow denotes the point of attachment to the ringincorporating the radical A;

R₄ is trifluoromethyl, trifluoromethylsulfanyl ortrifluoromethylsulfonyl; and

G₁ is N and G₂ is CH, G₁ is CH and G₂ is N, G₁ and G₂ are CH, or G₁ andG₂ are N; preferably G₁ is CH and G₂ is N.

In another aspect the present invention provides a compositioncomprising an insecticidally, acaricidally, nematicidally ormolluscicidally effective amount of a compound of formula (I), or anagrochemically acceptable salt, stereoisomer, enantiomer, tautomer orN-oxide thereof, as defined in any of the foregoing embodiments 1-19,and, optionally, an auxiliary or diluent.

In a further aspect the present invention provides a method of combatingand controlling insects, acarines, nematodes or molluscs which comprisesapplying to a pest, to a locus of a pest, or to a plant susceptible toattack by a pest an insecticidally, acaricidally, nematicidally ormolluscicidally effective amount of a compound of formula (I), or anagrochemically acceptable salt, stereoisomer, enantiomer, tautomer orN-oxide thereof, as defined in any of the foregoing embodiments 1-19 ora composition as defined above.

In a yet further aspect the present invention provides a method for theprotection of plant propagation material from the attack by insects,acarines, nematodes or molluscs, which comprises treating thepropagation material or the site, where the propagation material isplanted, with a composition as defined above.

The process according to the invention for preparing compounds offormula (I) is carried out in principle by methods known to thoseskilled in the art. The subgroup of compounds of the formula I wherein nis 0, i.e. sulfilimine Ia, wherein R₁, R₂, R₃, A, and Q are as definedabove, may be prepared by reacting the corresponding sulfide of theformula II, wherein R₁, R₂, R₃, A, and Q are as defined above, underimination reaction conditions (step A, Scheme 1). The particularsubgroup of compounds of the formula I wherein n is 1, defined as thesulfoximine I, wherein R₁, R₂, R₃, A, and Q are as defined above, may beobtained by oxidation of the sulfilimine compounds of the formula Ia,wherein R₁, R₂, R₃, A, and Q are as defined above (step B).

Conversely, the order of the two steps may be reverted whereby thesulfoximine compounds of the formula I, wherein R₁, R₂, R₃, A, and Q areas defined above are as defined above, may be prepared from sulfoxidesof the formula III, wherein R₁, R₂, R₃, A, and Q are as defined above,under appropriate imination reaction conditions (step A′).

Typical preparation methods and reaction conditions to access thecompounds of the formula I, either towards the sulfilimines Ia (step A)or the sulfoximines I (step A′), may be found, for example, in H.Okamura, C. Bolm, Org. Lett., 2004, 6, 1305-1307; H. Okamura, C. Bolm,Chem. Lett., 2004, 33, 482-487; D. Leca, K. Song, M. Amatore, L.Fensterbank, E. Lacôte, M. Malacria, Chem. Eur. J., 2004, 10, 906-916;or M. Reggelin, C. Zur, Synthesis, 2000, 1-64. Typical iminationreagents/conditions may be defined as NaN₃/H₂SO₄,O-mesitylenesulfonyl-hydroxylamine (MSH), or metal-catalyzed methods[see O. G. Mancheno, C. Bolm, Chem. Eur. J., 2007, 13, 6674-6681] suchas R₂—N₃/FeCl₂, R₂—NH₂/Fe(acac)₃/PhI═O, PhI═N—R₂/Fe(OTf)₂,PhI═N—R₂/CuOTf, PhI═N—R₂/Cu(OTf)₂, PhI═N—R₂/CuPF₆,PhI(OAc)₂/R₂—NH₂/MgO/Rh₂(OAc)₄ or oxaziridines (e.g.3-(4-cyano-phenyl)-oxaziridine-2-carboxylic acid tert-butyl ester).

Of particular interest are metal-free imination methods of sulfides ofthe formula II and/or sulfoxides of the formula III to preparesulfilimines of the formula Ia (step A) and/or sulfoximines of theformula I (step A′). Such imination reactions involve R₂—NH₂ and anoxidant, for example, PhI(OAc)₂/R₂—NH₂ as described in G. Y. Cho, C.Bolm, Tetrahedron Lett., 2005, 46, 8007-8008; or N-bromosuccinimide(NBS)/R₂—NH₂ and a base such as sodium or potassium ter-butoxide asdescribed in C. Bolm et al., Synthesis, 2010, No 17, 2922-2925. Oxidantssuch as N-iodosuccinimide (NIS) or iodine may be also used alternativelyas described, for example, in O. G. Mancheno, C. Bolm, Org. Lett. 2007,9, 3809-3811. An example of hypochlorite salts being used as oxidant,such as sodium hypochlorite NaOCI or calcium hypochlorite Ca(OCl)₂, wasdescribed in WO2008/106006.

For the transformation of a sulfilimine Ia to a sulfoximine I (step B),classical oxidation reagents may involve, for example, KMnO₄, NaMnO₄,mCPBA, NaIO₄/RuO₂, NaIO₄/RuCl₃, H₂O₂, oxone. In particular, the use ofruthenium salts in combination with alkali metal periodates andalternatively the use of alkali metal permanganates was described inWO2008/097235 and WO2008/106006.

Detailed preparation conditions useful for the synthesis of suchsulfilimine and/or sulfoximine compounds of formula Ia respectively Iare also given, for example, in WO2006/061200 or WO 2007/080131.

Alternatively, the subgroup of sulfoximine compounds of the formula Iwherein R₂ is hydrogen and n is 1, and in which R₁, R₃, A, and Q are asdefined in formula I,

can be prepared (scheme 1a) by reacting sulfide compounds of formula II,wherein R₁, R₃, A, and Q are as defined in formula I, with a suitablenitrogen source such as, for example, ammonia, ammonium carbamate orammonium acetate (preferably ammonium carbamate), in the presence ofhypervalent iodine reagents, such as diacetoxyiodobenzene, in solventssuch as toluene, acetonitrile or methanol, at temperatures between 0 and100° C., preferably around room temperature, in analogy to descriptionsfound, for example, in Chem. Commun. 53, 348-351; 2017 (and referencescited therein).

A compound of the formula Ib, wherein R₁, R₃, A, and Q are as definedabove and wherein n is 1 and R₂ is CN, may be transformed into acompound of the formula Ic, wherein R₁, R₃, A, and Q are as definedabove are as defined above and wherein n is 1 and R₂ is C(O)CF₃, bytreatment with trifluoroacetic anhydride in a solvent such asdichloromethane as described, for example, in O. G. Mancheno, C. Bolm,Org. Lett. 2007, 9, 3809-3811. The compound of the formula Ic, whereinR₁, R₃, A, and Q are as defined above and wherein n is 1 and R₂ isC(O)CF₃, may be transformed into a compound of the formula I, whereinR₁, R₃, A, and Q are as defined above and wherein n is 1 and R₂ ishydrogen, by treatment with a base such as sodium or potassium carbonatein a polar protic solvent such as methanol or ethanol as described, forexample, in H. Okamura, C. Bolm, Org. Lett. 2004, 6, 1305-1307. Acompound of the formula Id, wherein R₁, R₃, A, and Q are as definedabove are as defined above and wherein n is 1 and R₂ is C(O)NH₂, may beprepared from a compound of the formula Ib, wherein R₁, R₃, A and Q areas defined above and wherein n is 1 and in which R₂ is CN, by treatmentwith a strong acid such as concentrated sulfuric acid in an organicsolvent such as acetonitrile as described, for example, in WO09/111309.The chemistry is summarised in scheme 2.

A compound of the formula Ie, wherein R₁, R₃, A and Q are as definedabove and wherein n is 1 and R₂ is C₁-C₆alkyl, may be prepared from acompound of the formula I, wherein R₁, R₃, A and Q are as defined aboveand wherein n is 1 and in which R₂ is hydrogen, by treatment with analkylating agent of formula LG-R₂, wherein LG is a leaving group such asa halogen (especially bromine or iodine), a sulfonate OSO₂R₁₂(especially mesylate or tosylate), wherein R₁₂ is C₁-C₆alkyl,C₁-C₆halo-alkyl, or phenyl optionally substituted by nitro orC₁-C₃alkyl, or a sulfate (such as dimethylsulfate), preferably in thepresence of a suitable base, such as alkali metal carbonates, forexample sodium carbonate or potassium carbonate, or alkali metalhydrides such as sodium hydride, or alkali metal hydroxides such assodium hydroxide and potassium hydroxide, in an inert solvent attemperatures between −20 and 150° C., preferably between 0 and 80° C.Examples of solvent to be used include ethers such as tetrahydrofuran,ethylene glycol dimethyl ether (1,2-dimethoxyethane), tert-butylmethylether, and 1,4-dioxane, aromatic hydrocarbons such as toluene andxylene, nitriles such as acetonitrile or polar aprotic solvents such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone ordimethyl sulfoxide.

A compound of the formula If, wherein R₁, R₃, A and Q are as definedabove and wherein n is 1 and R₂ is C(O)R₇ and R₇ is C₁-C₆alkyl orC₁-C₆haloalkyl, may be prepared from a compound of the formula I,wherein R₁, R₃, A and Q are as defined above and wherein n is 1 and R₂is hydrogen, by treatment with a reagent of formula LG₁-C(O)R₇ or ananhydride reagent of formula R₇C(O)—O—C(O)R₇, wherein R₇ is as definedabove and LG₁ is a leaving group such as a halogen (especiallychlorine), optionally in presence of an acylating catalyst, such as4-dimethylaminopyridine (DMAP), preferably in presence of a base, suchas triethylamine, diisopropylethylamine or pyridine, in an inert solventat temperatures between 0 and 50° C. Examples of solvent to be usedinclude ethers such as tetrahydrofuran, ethylene glycol dimethyl ether,tert-butylmethyl ether, and 1,4-dioxane, aromatic hydrocarbons such astoluene and xylene, halogenated hydrocarbons such as dichloromethane andchloroform, nitriles such as acetonitrile or polar aprotic solvents suchas N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidoneor dimethyl sulfoxide. The reaction may be carried out in the presenceof an excess of base, which then may also act as a solvent or diluent.

A compound of the formula Ig, wherein R₁, R₃, A and Q are as definedabove and wherein n is 1 and in which R₂ is C(O)OR₈ and R₈ isC₁-C₆alkyl, C₁-C₆haloalkyl may be prepared from a compound of theformula I, wherein R₁, R₃, A and Q are as defined above and wherein n is1 and R₂ is hydrogen, by treatment with a reagent of formulaLG₂-C(O)OR₈, wherein R₈ is as defined above and LG₂ is a leaving groupsuch as a halogen (especially chlorine), optionally in presence of anacylating catalyst, such as 4-dimethylaminopyridine (DMAP), preferablyin presence of a base, such as triethylamine, diisopropylethylamine orpyridine, in an inert solvent at temperatures between 0 and 50° C.Examples of solvent to be used include ethers such as tetrahydrofuran,ethylene glycol dimethyl ether, tert-butylmethyl ether, and 1,4-dioxane,aromatic hydrocarbons such as toluene and xylene, halogenatedhydrocarbons such as dichloromethane and chloroform, nitriles such asacetonitrile or polar aprotic solvents such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide. Thereaction may be carried out in the presence of an excess of base, whichthen may also act as a solvent or diluent.

A compound of the formula Ih, wherein R₁, R₃, A, and Q are as definedabove and wherein n is 1 and which R₂ is CONR₉R₁₀ and R₉, R₁₀independently of one another are hydrogen or C₁-C₆alkyl, may be preparedfrom a compound of the formula I, wherein R₁, R₃, A and Q are as definedabove and wherein n is 1 and in which R₂ is hydrogen, by treatment witha reagent of formula LG₃-C(O)NR₉R₁₀, wherein R₉ and R₁₀ are as definedabove and LG₃ is a leaving group such as a halogen (especiallychlorine), optionally in presence of an acylating catalyst, such as4-dimethylaminopyridine (DMAP), preferably in presence of a base, suchas triethylamine, diisopropylethylamine or pyridine, in an inert solventat temperatures between 0 and 50° C. Examples of solvent to be usedinclude ethers such as tetrahydrofuran, ethylene glycol dimethyl ether,tert-butylmethyl ether, and 1,4-dioxane, aromatic hydrocarbons such astoluene and xylene, halogenated hydrocarbons such as dichloromethane andchloroform, nitriles such as acetonitrile or polar aprotic solvents suchas N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidoneor dimethyl sulfoxide. The reaction may be carried out in the presenceof an excess of base, which then may also act as a solvent or diluent.

A compound of the formula Ii, wherein R₁, R₃, A, and Q are as definedabove and wherein n is 1 and in which R₂ is SO₂R₁₁ and R₁₁ isC₁-C₆alkyl, may be prepared from a compound of the formula I, whereinR₁, R₃, A and Q are as defined above and wherein n is 1 and in which R₂is hydrogen, by treatment with a reagent of formula LG₄-SO₂R₁₁, whereinR₁₁ is as defined above and LG₄ is a leaving group such as a halogen(especially chlorine), optionally in presence of an acylating catalyst,such as 4-dimethyl-aminopyridine (DMAP), preferably in presence of abase, such as triethylamine, diisopropylethylamine or pyridine, in aninert solvent at temperatures between 0 and 50° C. Examples of solventto be used include ethers such as tetrahydrofuran, ethylene glycoldimethyl ether, tert-butylmethyl ether, and 1,4-dioxane, aromatichydrocarbons such as toluene and xylene, halogenated hydrocarbons suchas dichloromethane and chloroform, nitriles such as acetonitrile orpolar aprotic solvents such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide. Thereaction may be carried out in the presence of an excess of base, whichthen may also act as a solvent or diluent. A compound of the formula Ij,wherein R₁, R₂, R₃, and Q are as defined above and wherein n is 1 and inwhich R₂ is C(O)R₇ and R₇ is hydrogen, may be prepared from a compoundof the formula I, wherein R₁, R₃, A and Q are as defined above andwherein n is 1, and R₂ is hydrogen, by treatment with a trialkylorthoformate, such as trimethyl orthoformate, optionally in the presenceof an acid activator such as para-toluenesulfonic acid, optionally inthe presence of an inert organic solvent, and at temperatures between 0and 180° C. The reaction may be carried out in the presence of an excessof trialkyl orthoformate, which then may also act as a solvent ordiluent. Such a process is illustrated, for example, in WO 2006/037945.The transformations described above are illustrated in scheme 3.

Compounds of formula II wherein R₃ is hydrogen are in some cases known,for example:2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(trifluoromethoxy)-1,3-benzoxazole,CAS [2128705-99-5], WO 2017146226;2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(difluoromethylsulfanyl)-1,3-benzoxazole,CAS [2128706-06-7], WO 2017146226;2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(difluoromethoxy)-1,3-benzoxazole,CAS [2128706-01-2], WO 2017146226;5-cyclopropyl-2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one,CAS [2098699-63-7], WO 2017089190;5-cyclopropyl-2-(4-cyclopropyl-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one,CAS [2098699-80-8], WO 2017089190;2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(1,1,2,2,2-pentafluoroethyl)-1,3-benzoxazole,CAS [1975147-97-7], WO 2016121997;2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(trifluoromethylsulfanyl)-1,3-benzoxazole,CAS [1975147-94-4], WO 2017146226;2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-1-methyl-5-(trifluoromethyl)benzimidazole,CAS [1975147-91-1], WO 2016121997;2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)oxazolo[5,4-b]pyridine,CAS [1975147-87-5], WO 2016121997;2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(1,1,2,2,2-pentafluoroethyl)imidazo[4,5-b]pyridine,CAS [1975147-85-3], WO 2016121997;6-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-methyl-3-(2,2,2-trifluoroethoxy)imidazo[4,5-c]pyridazine,CAS [1957168-99-8], WO 2016104746;2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine,CAS [1951416-89-9], WO 2016096584;2-(4-cyclopropyl-2-ethylsulfanyl-phenyl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine,CAS [1923785-41-4], WO 2016071214;2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine,CAS [1923784-36-4], WO 2016071214;2-(4-cyclopropyl-2-ethylsulfanyl-phenyl)-5-ethyl-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one,CAS [1879051-89-4], WO 2016023954;2-(4-cyclopropyl-2-ethylsulfanyl-phenyl)-3,5-dimethyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one,CAS [1879051-88-3], WO 2016023954.

Compounds of formula II wherein R₃ is H, i.e compounds of formula IIa

can be generally prepared by reaction of a compound of formula IV,wherein A, Q and R₁ are as defined in formula I above, with a compoundof formula V as shown in scheme 4:

More specifically, compounds of formula IIa can be prepared (as depictedin scheme 4) by reacting compounds of formula IIa with compounds offormula V, wherein X_(b1) can be a halogen, preferentially chlorine,bromine or iodine and Y_(b1) can be a boron-derived functional group, asfor example B(OH)₂ or B(OR_(b1))₂ wherein R_(b1) can be a C₁-C₆alkylgroup or the two groups OR_(b1) can form together with the boron atom afive- or six-membered ring, as for example a pinacol boronic ester(Suzuki cross-coupling, see for example Tetrahedron Letters, 43(39),6987-6990; 2002). In formula IIa, A, R₁ and Q are as described informula I. The reaction can be catalyzed by a palladium based catalyst,for example tetrakis(triphenylphosphine) palladium(0),bis(triphenylphosphine)palladium(II) dichloride,chloro(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II)(XPhos palladacycle),(1,1′bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane(1:1 complex) or palladium acetate plus phosphine ligands (such as, forexample, triphenylphosphine or tricyclohexylphosphine) in presence of abase, like sodium carbonate, tripotassium phosphate or cesium fluoride,in a solvent (such as toluene, 1,2-dimethoxy-ethane DME, tetrahydrofuranor dioxane) or a solvent mixture, like, for example a mixture of1,2-dimethoxyethane (or dioxane, toluene, or tetrahydrofuran) and water,preferably under inert atmosphere. The reaction temperature canpreferably range from ambient temperature to the boiling point of thereaction mixture, or alternatively heating may be performed undermicrowave irradiation.

Alternatively, compounds of formula IV, wherein X_(b1) can be a halogen,preferentially chlorine, bromine or iodine, may be reacted withcompounds of formula V, wherein Y_(b1) is a magnesium halide group, suchas —MgBr (Kumada cross-coupling), optionally in the presence ofadditives, such as zind halides (Journal of Organic Chemistry, 75(19),6677-6680; 2010). The reaction may be catalyzed by a palladium basedcatalyst, or may involve a nickel based catalyst, such as1,3-is(diphenylphosphino) propanenickel dichloride (dppp)NiCl₂.

Also known are reactions between compounds of formula IV with compoundsof formula V, wherein Y_(b1) is a zinc halide group, such as —ZnBr(Negishi cross-coupling), as illustrated for example in SyntheticCommunications, 28(2), 225-232; 1998. The reaction may be catalyzed by apalladium based catalyst, such as for example,(1,1′bis(diphenylphosphino)-ferrocene)dichloropalladium Pd(dppf)Cl₂ orbis(triphenylphosphine)palladium(II) dichloride, optionally in thepresence of phosphine additives (such as, for example,2-dicyclohexyl-phosphino-2′,6′-dimethoxy-biphenyl S-PHOS), in a solvent,like, for example 1,2-dimethoxyethane, dioxane, toluene, ortetrahydrofuran, preferably under inert atmosphere. The reactiontemperature can preferentially range from ambient temperature to theboiling point of the reaction mixture.

Compounds of formula II, wherein R₃ is cyano are in some cases known,for example:1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile,CAS [2225113-68-6], WO 2018/077565;1-[3-ethylsulfanyl-4-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile, CAS [CAS[2225113-73-3], WO 2018/077565;1-[4-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-ethylsulfanyl-phenyl]cyclopropanecarbonitrile,CAS [2098699-74-0], WO 2017/089190;1-[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]cyclopropanecarbonitrile,CAS [2098699-59-1], WO 2017/089190;1-[5-ethylsulfanyl-6-[5-(trifluoromethylsulfanyl)-1,3-benzoxazol-2-yl]-3-pyridyl]cyclopropanecarbonitrile,CAS [1975148-53-8], WO 2016/121997;1-[3-ethylsulfanyl-4-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]phenyl]cyclopropanecarbonitrile,CAS [1923785-47-0], WO 2016/071214;1-[5-ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]cyclopropanecarbonitrile,CAS [1923784-42-2], WO 2016/071214.

Other compounds of formula II, wherein R₃ is cyano and R₁, A, and Q areas defined in formula I, i.e compounds of formula IIb

can be prepared as shown in scheme 5:

As shown in scheme 5, treatment of compounds of formula IV, wherein R₁,Q₁ and A are as described in formula I, and wherein Xb₁ is preferablyhalogen (even more preferably chlorine, bromine or iodine), withtrimethylsilyl-acetonitrile TMSCN, in the presence of zinc(II)fluoride,and a palladium(0)catalyst such astris(dibenzylideneacetone)dipalladium(0)-chloroform adduct (Pd₂(dba)₃),a ligand, for example Xantphos, in an inert solvent, such as DMF attemperatures between 100-160° C., optionally under microwave heating,leads to compounds of formula VI. Such chemistry has been described inthe literature, e.g. in Org. Lett., 16(24), 6314-6317; 2014. Compoundsof formula IV can be treated with compounds of formula VII, wherein Xb₁is as described above, in the presence of a base such as sodium hydride,K₂CO₃, or Cs₂CO₃, in an inert solvent such as DMF, acetone, oracetonitrile, to give compounds of formula IIb. Alternatively, compoundsof formula IIb can be prepared directly from compounds of formula IV bytreatment with compounds of formula VIII with Pd₂(dba)₃, a ligand, suchas BINAP a strong base such as LiHMDS, in an inert solvent such as THEat temperatures between 40-70° C. Such chemistry has been described in,for example, J. Am. Chem. Soc., 127(45), 15824-15832; 2005.

Another process to compounds of formula IIb involves reaction ofcompounds of formula IV, wherein A, R₁ and Q are as described underformula I, and in which Xb₁ is halogen, preferably chlorine, bromine,iodine, with 4-isoxazoleboronic acid or 4-isoxazoleboronic acid pinacolester (compound of formula IX), in the presence of potassium fluorideKF, and a palladium catalyst such asbis(triphenylphosphine)palladium(II) dichloride Pd(PPh₃)₂Cl₂, in aninert solvent, such as dimethylsulfoxide DMSO, optionally in mixturewith water, at temperatures between 40-150° C., optionally undermicrowave heating, leads to compounds of formula IX, wherein Q, R₁ and Aare as described under formula I above. Reaction of compounds of formulaIX, with aqueous potassium fluoride KF (concentration between 0.5 and3M, preferably 1M), in an inert solvent, such as dimethylsulfoxide DMSOor methanol, at temperatures between 20-150° C., optionally undermicrowave heating, leads to compounds of formula VI, wherein A, R₁ and Qare as described under formula I above. Conversion of compounds offormula V to compounds of formula IIb is as described above. Suchchemistry has been described in the literature, e.g. in J Am Chem Soc2011, 133, 6948-6951. Compounds of the formula IIb may further beutilized for the preparation of compounds of formula II (scheme 6) whereR₃ is further functionalized. Indeed, compounds of formula IIb, whereinA, R₁, X₁ and R₂ are as defined in formula I above, may be partiallyhydrolyzed, under acidic or basic conditions known to persons skilled inthe art to compounds of formula IIc, or fully hydrolysed to compounds offormula IId. Treatment of compounds of formula IIc with reagents such asSF₄ or Fluolead (4-tert-butyl-2, 6-dimethyl phenylsulfur trifluoride),optionally in the presence of HF, leads to compounds of formula IIe (asdescribed in for example, Organic Letters, 16, 6314-6317; 2014.

Activation of compounds of formula (IId), wherein R₁, Q and A are asdefined in formula I, by methods known to those skilled in the art anddescribed in, for example, Tetrahedron, 2005, 61 (46), 10827-10852, toform an activated species (IIf), wherein Q, R₁ and A are as defined informula I, and wherein X₀ is halogen, preferably chlorine. For example,compounds (IIf) where X₀ is halogen, preferably chlorine, are formed bytreatment of (IId) with, for example, oxalyl chloride (COCl)₂ or thionylchloride SOCl₂ in the presence of catalytic quantities ofN,N-dimethylformamide DMF in inert solvents such as methylene chlorideCH₂Cl₂ or tetrahydrofuran THF at temperatures between 20 to 100° C.,preferably 25° C. Alternatively, treatment of compounds of formula(IIId) with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimideEDC or dicyclohexyl carbodiimide DCC will generate an activated species(XII), wherein X₀ is X₀₁ or X₀₂ respectively, in an inert solvent, suchas pyridine or tetrahydrofuran THF, optionally in the presence of abase, such as triethylamine, at temperatures between 50-180° C.; Suchactivated intermediates of formula IIf can be reacted with nucleophilessuch as amines of formula HNR₁₀₁R₀₁₂, wherein R₁₀₁ and R₁₀₂ are hydrogenor C₁-C₆alkyl, or HOR₁₀₃where R₁₀₃ is C₁-C₆alkyl, optionally in thepresence of a base such as triethylamine, pyridine or DMAP, in an inertsolvent such as CH₂Cl₂, THF or acetonitrile, to give compounds offormula IIg and IIh respectively. Such reactions are well known to thoseskilled in the art. The post transformation of the cyanocyclopropyls areillustrated in Scheme 6.

Compounds of the formula II, wherein Q is Q₁, defining compounds of theformula II-Q₁

wherein R₁, R₃, R₄, X₁, G₁, and G₂ are as defined in formula I can beprepared as shown in scheme 7.

As shown in scheme 7, compounds of formula II-Q₁ can be prepared bycyclizing compounds of the formula (XIV), wherein R₁, R₃, R₄, A, X₁, G₁,and G₂ are as defined in formula I, for example through heating inacetic acid or trifluoroacetic acid (preferably when X₁ is NR₅, whereinR₅ is C₁-C₄alkyl), at temperatures between 0 and 180° C., preferablybetween 20 and 150° C., optionally under microwave irradiation.Cyclization of compounds of formula (XIV) may also be achieved in thepresence of an acid catalyst, for example methanesulfonic acid, orpara-toluenesulfonic acid p-TsOH, in an inert solvent such as N-methylpyrrolidone, toluene or xylene, at temperatures between 25-180° C.,preferably 100-170° C. Such processes have been described previously,for example, in WO 2016096584. Alternatively, compounds of formula (XIV)may be converted into compounds of formula II-Q₁ (preferably when X₁ isO) using triphenylphosphine, di-isopropyl azodicarboxylate (or di-ethylazodicarboxylate) in an inert solvent such as tetrahydrofuran THE attemperatures between 20-50° C. Such Mitsunobu conditions have beenpreviously described for these transformations (see WO 2009/131237 andWO 2016/121997).

Compounds of the formula (XIV), wherein R₁, R₃, R₄, A, X₁, G₁, and G₂are as defined in formula I, may be prepared via acylation by;

i) Activation of compounds of formula (XIII), wherein R₁, R₃ and A areas defined in formula I, by methods known to those skilled in the artand described in, for example, Tetrahedron, 2005, 61 (46), 10827-10852,to form an activated species (XII), wherein R₁, R₃ and A are as definedin formula I, and wherein X₀ is halogen, preferably chlorine. Forexample, compounds (XII) where X₀ is halogen, preferably chlorine, areformed by treatment of (XIII) with, for example, oxalyl chloride (COCl)₂or thionyl chloride SOCl₂ in the presence of catalytic quantities ofN,N-dimethylformamide DMF in inert solvents such as methylene chlorideCH₂Cl₂ or tetrahydrofuran THE at temperatures between 20 to 100° C.,preferably 25° C. Alternatively, treatment of compounds of formula(XIII) with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimideEDC or dicyclohexyl carbodiimide DCC will generate an activated species(XII), wherein X₀ is X₀₁ or X₀₂ respectively, in an inert solvent, suchas pyridine or tetrahydrofuran THF, optionally in the presence of abase, such as triethylamine, at temperatures between 50-180° C.;followed by

ii) Treatment of the activated species (XII) with compounds of theformula (XI), wherein X₁, G₁, G₂ and R₄ are as defined in formula I, inthe presence of a base, such as triethylamine,N,N-diisopropyl-ethyl-amine or pyridine, in an inert solvents such asdichloromethane, tetrahydrofuran, dioxane, N,N-dimethylformamide,N,N-dimethylacetamide, acetonitrile, ethyl acetate or toluene, attemperatures between 0 and 50° C., to form the compounds of formula(XIV). Compounds of formula XIII where R₃ is H, i.e compound wherein isR₁ is ethyl, R₃ is H, and A is N or CH are known and described in WO2017146226, or WO 2016121997 (for5-cyclopropyl-3-ethylsulfanyl-pyridine-2-carboxylic acid, CAS[1975148-58-3], and WO 2016023954 (for4-cyclopropyl-2-ethylsulfanyl-benzoic acid, CAS [1879052-58-0]. Thecompound of formula XIII wherein R₃ is cyano, R₁ is ethyl and A is CH(4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid, CAS[2225113-79-9]), and the compound of formula XIII wherein R₃ is cyano,R₁ is ethyl and A is N(5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid, CAS[2225113-77-7]) are known and described in and described in WO2018/077565.

Compounds of formula (XI), wherein X₁, G₁, G₂ and R₂ are as defined informula I, have been previously described, for example, in WO2012/086848, WO 2015/000715, and WO 2016/116338.

Compounds of the formula II, wherein Q is Q₂, defining compounds of theformula II-Q₂, wherein R₁, R₃, R₄, A, and G₂ are as defined in formulaI,

may be prepared (scheme 8) by condensing compounds of the formula (XVI),wherein R₁, R₃, A are as defined in formula I, and in which Xc is is aleaving group such as, for example, chlorine, bromine or iodine(preferably chlorine or bromine), with compounds of the formula (XVI),wherein G₂ and R₂ are as defined in formula I, in an inert solvent, forexample ethanol or acetonitrile, optionally in the presence of asuitable base, such as sodium, potassium or cesium carbonate, ormagnesium oxide at temperatures between 80 and 150° C., optionally undermicrowave heating conditions. Such processes have been describedpreviously, for example, in WO 2012/49280 or WO 2003/031587. Compoundsof formula (XV), wherein G₂ and R₂ are as defined in formula I, areeither known compounds, commercially available or may be prepared byknown methods known to those skilled in the art.

Compounds of the formula (XVI), wherein R₁, R₃, and A are as defined informula I, and in which Xc is is a leaving group such as, for example,chlorine, bromine or iodine (preferably chlorine or bromine),

may be prepared (scheme 9) by treatment of compounds of formula (XVIII),wherein R₁, R₃, and A are as defined in formula I, with a halogenatingagent (“Xc*” source), e.g. N-bromosuccinimide, N-iodosuccinimide,N-chlorosuccinimide, 12, CuBr₂, Br₂ in acetic acid, PhNMe₃ ⁺Br₃ ⁻,typically in a solvent such as methanol, acetonitrile, tetrahydrofurane,ethyl acetate, chloroform or dichloromethane, or mixtures thereof, attemperatures between 0° C. and 150° C., preferably between roomtemperature and 120° C., optionally under microwave heating conditions.Such processes have been described previously, for example, inWO2016/071214.

Compounds of formula (XVIII), wherein R₁, R₃ and A are as defined informula I, may be prepared by reacting compounds of formula (XVII),wherein R₁ and A are as defined in formula I, and in which Xa is aleaving group such as, for example, chlorine, bromine or iodine(preferably chlorine or bromine), under conditions already describedabove (see scheme 5, transformation of compounds IV into IIb).

Compounds of formula (XVII), wherein R₁ and A are as defined in formulaI, and wherein Xa is a leaving group such as, for example, chlorine,bromine or iodine, in particular those compounds wherein Xa is a halogen(even more preferably chlorine, bromine or iodine; particularlypreferred is chlorine or bromine), are either known compounds,commercially available or may be prepared by known methods, described inthe literature, as for example in WO 2016/071214.

Alternatively, compounds of the formula II, wherein Q is Q₅, definingcompounds of the formula II-Q₅, wherein R₁, R₃, R₄, R₆ and A are asdefined in formula I,

may be prepared (scheme 9a) by cyclizing compounds of the formula (XXa),wherein R₁, R₃, R₄, R₅, R₆, and A are as defined in formula I, orregioisomers of the formula (XXb) with identical substituentdefinitions, or a mixture thereof in any ratio, under conditions alreadydescribed above (see scheme 7, transformation of compounds (XIV) intoII-Q₁).

Compounds of the formula (XXa), wherein R₁, R₃, R₄, R₅, R₆, and A are asdefined in formula I, or regioisomers of the formula (XXb) withidentical substituent definitions, or a mixture thereof in any ratio,may be prepared by treatment of the activated species (XII) describedabove with compounds of the formula (XIX), wherein R₄, R₅ and R₆ are asdefined in formula I, under conditions already described above (seescheme 7, transformation of compounds (XII) and (XIII) into compounds(XIV)).

Compounds of formula (XIX), wherein R₄, R₅ and R₆ are as defined informula I, have been previously described, for example, in WO2016/023954, WO 2016/142326, WO 2017/133994, and WO 2018077565

Alternatively, compounds of the formula II, wherein Q is Q₃, definingcompounds of the formula II-Q₃, wherein R₁, R₄, R₃, and A are as definedin formula I,

may be prepared (scheme 10) by condensing compounds of the formula (XVI)described above, wherein R₁, R₃ and A are as defined in formula I, andin which Xc is a leaving group such as, for example, chlorine, bromineor iodine (preferably chlorine or bromine), with compounds of theformula (XXI), wherein R₄ is as defined in formula I, in an inertsolvent, for example ethanol, toluene or acetonitrile, optionally in thepresence of a suitable base, such as sodium, potassium or cesiumcarbonate (or sodium or potassium hydrogen carbonate), or magnesiumoxide at temperatures between 80 and 150° C., optionally under microwaveheating conditions. Such processes have been described previously, forexample, in WO 2011/074658. Compounds of formula (XXI), wherein R₄ is asdefined in formula I, are either known compounds, commercially availableor may be prepared by known methods known to those skilled in the art(see for example WO 2011/074658 and WO 2010/083145).

Compounds of the formula II, wherein Q is Q₄, defining compounds of theformula II-Q₄,

wherein R₁, R₃, R₄, G₁, G₂ and A are as defined in formula I,

may also be prepared (scheme 11) via N—N bond forming reaction of azidoimines of compounds of the formula (XXV), wherein R₁, R₄, R₇, R₈, A, G₁,G₂ and R₂ are as defined in formula I, under pyrolytic condition whichfacilitates extrusion of N2. Alternatively, this reaction may beconducted in presence of a metal catalyst, for example a Cu(I) catalyst,such as CuI, CuBr, CuCl or CuCN, or more generally with transitionmetals, in combination with a ligand such as tetramethylethylenediamine,2,2′-bipyridine or 1,10-phenanthroline. Suitable solvents may includeuse of e toluene, chlorobenzene, or xylene, at temperatures between roomtemperature and 200° C., preferably between 100 and 160° C., optionallyunder microwave heating conditions. Such reductive cyclisation reactionconditions were described in, for example, Organic Letters, 2011, Vol.13, No. 13, 3542-3545, and US 2017/0260183,

Compounds of the formula (XXV), wherein R₁, R₃, R₄, G₁, G₂ and A are asdefined in formula I, may be prepared by reaction between compounds offormula (XXIII), wherein R₁, R₃ and A are as defined in formula I, andcompounds of formula (XXIV), wherein G₁, G₂ and R₄ are as defined informula I, usually upon heating at temperatures between room temperatureand 200° C., preferably between 40 and 160° C., optionally undermicrowave heating conditions, in suitable solvents that may include, forexample, toluene or xylene. The formation of compounds of formula (XXV)may require water removal, either by azeotropical distillation, or bymeans of a drying agent such as for example TiCl₄ or molecular sieves.Such formation of Schiff bases of formula (XXV) is known to thoseskilled in the art, and was described in, for example, WO 2017/134066.Compounds of formula XXIV are reported in literature (see CAS2211908-96-0 reported in WO 2018/052136).

Compounds of the formula XXIII, may be prepared by the reaction ofcompound of formula XXII in the presence of acid such as HCl, H₂SO₄,H₃PO₄, HNO₃, TFA. Such deprotection reaction of N-linked carbamate arewell known to those skilled in the art and described for example in RSCAdvances, 5(5), 3200-3205; 2015

Compounds of formula XXII, may be prepared by the reaction of compoundsof formula XIII and organo-azide or an ammonia derivatives for exampleNH₄OH, NH₃, NH₂Boc in the presence of a suitable base and in thepresence or absence of Lewis acids and solvent at temperatures between50° C. and 200° C. Examples of organo-azide include TMSN₃, sodium azide,diphenyl phosphoryl azide or tosyl azide and suitable solvent may bet-BuOH, toluene, xylene, THE or acetonitrile. Example of suitable Lewisacid may include Zn(OTf)₂. Such reactions of converting carboxylic acidsto amines are well known to those skilled in the art by the name ofCurtius reaction and reported in Org. Lett., 2005, 7, 4107-4110; Journalof Medicinal Chemistry, 49(12), 3614-3627; 2006.

Alternatively, compounds of the formula II-Q₄, wherein R₁, R₃, R₄, G₁,G₂ and A are as defined in formula I, may be prepared by reactingcompounds of formula (XXVI), wherein R₄, G₁, G₂ are as defined informula I, and in which LG is a leaving group such as, for example,chlorine, bromine or iodine (preferably chlorine or bromine), or anaryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonate,with compounds of formula (XXVII), wherein G₁, G₂ and R₄ are as definedin formula I, in the presence of base such as for example cesium,sodium, potassium or lithium carbonate, or sodium hydride, optionally inthe presence of a metal catalyst such as copper(I) iodide or a palladiumcatalyst, with or without additives such as L-proline,N,N′-dimethylethylenediamine or a phosphorus-based ligand, in an inertsolvent such as acetonitrile, N,N-dimethylformamide,N-methyl-2-pyrrolidone or dimethyl sulfoxide at temperatures betweenroom temperature and 200° C., optionally under microwave heatingconditions. Such aromatic nucleophilic substitution reaction conditionswere described in, for example, WO 2017/134066. Compounds of formulaXXVII may be obtained by a Sandmeyer reaction, i.e. diazotation ofcompound XXIII with NaNO2 or tBu-ONO in an inert solvent such as t-BuOHor water, followed by addition of an inoraganic halaide such as CuBr2,CuCl, or KI. Such Sandmeyer reactions are well known in the literature(see for example Synthesis, 2007, 2534-2538, Org. Lett., 2008, 10,3961-3964, and references cited therein.

The reactants can be reacted in the presence of a base. Examples ofsuitable bases are alkali metal or alkaline earth metal hydroxides,alkali metal or alkaline earth metal hydrides, alkali metal or alkalineearth metal amides, alkali metal or alkaline earth metal alkoxides,alkali metal or alkaline earth metal acetates, alkali metal or alkalineearth metal carbonates, alkali metal or alkaline earth metaldialkylamides or alkali metal or alkaline earth metal alkylsilylamides,alkylamines, alkylenediamines, free or N-alkylated saturated orunsaturated cycloalkylamines, basic heterocycles, ammonium hydroxidesand carbocyclic amines. Examples which may be mentioned are sodiumhydroxide, sodium hydride, sodium amide, sodium methoxide, sodiumacetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide,potassium carbonate, potassium hydride, lithium diisopropylamide,potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine,diisopropylethylamine, triethylenediamine, cyclohexylamine,N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine,4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU).

The reactants can be reacted with each other as such, i.e. withoutadding a solvent or diluent. In most cases, however, it is advantageousto add an inert solvent or diluent or a mixture of these. If thereaction is carried out in the presence of a base, bases which areemployed in excess, such as triethylamine, pyridine, N-methylmorpholineor N,N-diethylaniline, may also act as solvents or diluents.

The reaction is advantageously carried out in a temperature range fromapproximately −80° C. to approximately +140° C., preferably fromapproximately −30° C. to approximately +100° C., in many cases in therange between ambient temperature and approximately +80° C.

A compound of formula I can be converted in a manner known per se intoanother compound of formula I by replacing one or more substituents ofthe starting compound of formula I in the customary manner by (an)othersubstituent(s) according to the invention.

Depending on the choice of the reaction conditions and startingmaterials which are suitable in each case, it is possible, for example,in one reaction step only to replace one substituent by anothersubstituent according to the invention, or a plurality of substituentscan be replaced by other substituents according to the invention in thesame reaction step.

Salts of compounds of formula I can be prepared in a manner known perse. Thus, for example, acid addition salts of compounds of formula I areobtained by treatment with a suitable acid or a suitable ion exchangerreagent and salts with bases are obtained by treatment with a suitablebase or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in the customary mannerinto the free compounds I, acid addition salts, for example, bytreatment with a suitable basic compound or with a suitable ionexchanger reagent and salts with bases, for example, by treatment with asuitable acid or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in a manner known perse into other salts of compounds of formula I, acid addition salts, forexample, into other acid addition salts, for example by treatment of asalt of inorganic acid such as hydrochloride with a suitable metal saltsuch as a sodium, barium or silver salt, of an acid, for example withsilver acetate, in a suitable solvent in which an inorganic salt whichforms, for example silver chloride, is insoluble and thus precipitatesfrom the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds offormula I, which have salt-forming properties can be obtained in freeform or in the form of salts.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can be present inthe form of one of the isomers which are possible or as a mixture ofthese, for example in the form of pure isomers, such as antipodes and/ordiastereomers, or as isomer mixtures, such as enantiomer mixtures, forexample racemates, diastereomer mixtures or racemate mixtures, dependingon the number, absolute and relative configuration of asymmetric carbonatoms which occur in the molecule and/or depending on the configurationof non-aromatic double bonds which occur in the molecule; the inventionrelates to the pure isomers and also to all isomer mixtures which arepossible and is to be understood in each case in this sense hereinaboveand hereinbelow, even when stereochemical details are not mentionedspecifically in each case.

Diastereomer mixtures or racemate mixtures of compounds of formula I, infree form or in salt form, which can be obtained depending on whichstarting materials and procedures have been chosen can be separated in aknown manner into the pure diasteromers or racemates on the basis of thephysicochemical differences of the components, for example by fractionalcrystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in asimilar manner can be resolved into the optical antipodes by knownmethods, for example by recrystallization from an optically activesolvent, by chromatography on chiral adsorbents, for examplehigh-performance liquid chromatography (HPLC) on acetyl cellulose, withthe aid of suitable microorganisms, by cleavage with specific,immobilized enzymes, via the formation of inclusion compounds, forexample using chiral crown ethers, where only one enantiomer iscomplexed, or by conversion into diastereomeric salts, for example byreacting a basic end-product racemate with an optically active acid,such as a carboxylic acid, for example camphor, tartaric or malic acid,or sulfonic acid, for example camphorsulfonic acid, and separating thediastereomer mixture which can be obtained in this manner, for exampleby fractional crystallization based on their differing solubilities, togive the diastereomers, from which the desired enantiomer can be setfree by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to theinvention not only by separating suitable isomer mixtures, but also bygenerally known methods of diastereoselective or enantioselectivesynthesis, for example by carrying out the process according to theinvention with starting materials of a suitable stereochemistry.

N-oxides can be prepared by reacting a compound of the formula I with asuitable oxidizing agent, for example the H₂O₂/urea adduct in thepresence of an acid anhydride, e.g. trifluoroacetic anhydride. Suchoxidations are known from the literature, for example from J. Med.Chem., 32 (12), 2561-73, 1989 or WO 2000/15615.

It is advantageous to isolate or synthesize in each case thebiologically more effective isomer, for example enantiomer ordiastereomer, or isomer mixture, for example enantiomer mixture ordiastereomer mixture, if the individual components have a differentbiological activity.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can, if appropriate,also be obtained in the form of hydrates and/or include other solvents,for example those which may have been used for the crystallization ofcompounds which are present in solid form.

The compounds of formula I according to the following Tables Y-1 to Y-8,X-1 to X-8, U-1 to U-2 and V-1 to V-6 below can be prepared according tothe methods described above. The examples which follow are intended toillustrate the invention and show preferred compounds of formula I.

Tables Y-1 to Y-8 refer to compounds of formula

Table Z: Substituent definitions of R₃ and R₄:

Index R₄ R3 1 CF₃ CN 2 SCF₃ CN 3 SO₂CF₃ CN 4 CF₃ H 5 SCF₃ H 6 SO₂CF₃ H 7CF₃ CONH₂ 8 SCF₃ CONH₂

Table Y-1 provides 8 compounds Y-1.001 to Y-1.008 of formula IaY whereinA is CH, G₁ is CH, G₂ is CH and R₃, R₄ are as defined in table Z.

For example, compound Y-1.001 has the following structure;

Table Y-2 provides 8 compounds Y-2.001 to Y-2.008 of formula IaY whereinA is CH, G₁ is CH, G₂ is N and R₃, R₄ are as defined in table Z.

For example, compound Y-2.001 has the following structure;

Table Y-3 provides 8 compounds Y-3.001 to Y-3.008 of formula IaY whereinA is CH, G₁ is N, G₂ is CH and R₃, R₄ are as defined in table Z.

For example, compound Y-3.001 has the following structure;

Table Y-4 provides 8 compounds Y-4.001 to Y-4.008 of formula IaY whereinA is CH, G₁ is N, G₂ is N and R₃, R₄ are as defined in table Z.

For example, compound Y-4.001 has the following structure;

Table Y-5 provides 8 compounds Y-5.001 to Y-5.008 of formula IaY whereinA is N, G₁ is CH, G₂ is CH and R₃, R₄ are as defined in table Z.

For example, compound Y-5.001 has the following structure;

Table Y-6 provides 8 compounds Y-6.001 to Y-6.008 of formula IaY whereinA is N, G₁ is CH, G₂ is N and R₃, R₄ are as defined in table Z.

For example, compound Y-6.001 has the following structure;

Table Y-7 provides 8 compounds Y-7.001 to Y-7.008 of formula IaY whereinA is N, G₁ is N, G₂ is CH and R₃, R₄ are as defined in table Z.

For example, compound Y-7.001 has the following structure;

Table Y-8 provides 8 compounds Y-8.001 to Y-8.008 of formula IaY whereinA is N, G₁ is N, G₂ is N and R₃, R₄ are as defined in table Z.

For example, compound Y-8.001 has the following structure;

Tables X-1 to X-8 refer to compounds of formula

Table X-1 provides 8 compounds X-1.001 to X-1.008 of formula Iax whereinA is CH, G₁ is CH, G₂ is CH and R₃, R₄ are as defined in table Z.

For example, compound X-1.001 has the following structure;

Table X-2 provides 8 compounds X-2.001 to X-2.008 of formula Iax whereinA is CH, G₁ is CH, G₂ is N and R₃, R₄ are as defined in table Z.

Table X-3 provides 8 compounds X-3.001 to X-3.008 of formula Iax whereinA is CH, G₁ is N, G₂ is CH and R₃, R₄ are as defined in table Z.

Table X-4 provides 8 compounds X-4.001 to X-4.008 of formula Iax whereinA is CH, G₁ is N, G₂ is N and R₃, R₄ are as defined in table Z.

Table X-5 provides 8 compounds X-5.001 to X-5.008 of formula Iax whereinA is N, G₁ is CH, G₂ is CH and R₃, R₄ are as defined in table Z.

Table X-6 provides 8 compounds X-6.001 to X-6.008 of formula Ib whereinA is N, G₁ is CH, G₂ is N and R₃, R₄ are as defined in table Z.

Table X-7 provides 8 compounds X-7.001 to X-7.008 of formula Ib whereinA is N, G₁ is N, G₂ is CH and R₃, R₄ are as defined in table Z.

Table X-8 provides 8 compounds X-8.001 to X-8.008 of formula Ib whereinA is N, G₁ is N, G₂ is N and R₃, R₄ are as defined in table Z.

The tables V-1 to V-6 below illustrate specific compounds of theinvention of formula I (wherein R₂ is H, and n is 1).

Table V-1 provides 9 compounds V-1.001 to V-1.009 of formula I whereinis A is CH, R₃ is CN and Q are as defined in table W.

TABLE W Substituent definitions of Q: Index Q Index Q Index Q 1

4

7

2

5

8

3

6

9

For example compound V-1.002 has the following structure:

Table V-2 provides 9 compounds V-2.001 to V-2.009 of formula I wherein Ais N, R₃ is CN and Q are as defined in table W.

For example compound V-2.005 has the following structure:

Table V-3 provides 9 compounds V-3.001 to V-3.009 of formula I wherein Ais CH, R₃ is H and Q are as defined in table W.

For example compound V-3.008 has the following structure:

Table V-4 provides 9 compounds V-4.001 to V-4.009 of formula I wherein Ais N, R₃ is H and Q are as defined in table W.

For example compound V-4.001 has the following structure:

Table V-5 provides 9 compounds V-5.001 to V-5.009 of formula I wherein Ais CH, R₃ is CONH₂ and Q are as defined in table W.

For example compound V-5.007 has the following structure:

Table V-6 provides 9 compounds V-6.001 to V-6.009 of formula I wherein Ais N, R₃ is CONH₂ and Q are as defined in table W For example compoundV-6.006 has the following structure:

Tables U-1 to U-2 refer to compounds of formula

Table U-1 provides 8 compounds U-1.001 to U-1.008 of formula IaU whereinA is CH, and R₃, R₄ are as defined in table Z.

For example, compound U-1.001 has the following structure;

Table U-2 provides 8 compounds U-2.001 to U-2.008 of formula IaU whereinA is N, and R₃, R₄ are as defined in table Z.

The compounds of formula I according to the invention are preventivelyand/or curatively valuable active ingredients in the field of pestcontrol, even at low rates of application, which have a very favorablebiocidal spectrum and are well tolerated by warm-blooded species, fishand plants. The active ingredients according to the invention actagainst all or individual developmental stages of normally sensitive,but also resistant, animal pests, such as insects molluscs, nematodes orrepresentatives of the order Acarina. The insecticidal, molluscicidal,nematicidal or acaricidal activity of the active ingredients accordingto the invention can manifest itself directly, i. e. in destruction ofthe pests, which takes place either immediately or only after some timehas elapsed, for example during ecdysis, or indirectly, for example in areduced oviposition and/or hatching rate, a good activity correspondingto a destruction rate (mortality) of at least 50 to 60%.

Compounds of formula (I) according to the invention may possess anynumber of benefits including, inter alia, advantageous levels ofbiological activity for protecting plants against insects or superiorproperties for use as agrochemical active ingredients (for example,greater biological activity, an advantageous spectrum of activity, anincreased safety profile, improved physico-chemical properties, orincreased biodegradability or environmental profile). In particular, ithas been surprisingly found that certain compounds of formula (I) showan advantageous safety profile with respect to non-target organisms, forexample, non-target arthropods, in particular pollinators such as honeybees, solitary bees, and bumble bees. Most particularly, Apis mellifera.

In this regard, certain compounds of formula (I) of the invention can bedistinguished from known compounds by virtue of greater efficacy at lowapplication rates, which can be verified by the person skilled in theart using experimental procedures similar to or adapted from thoseoutlined in the biological examples, using lower application rates ifnecessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppmor 0.2 ppm.

Further it has surprisingly found that that compounds of formula (I)show advantageous physico-chemical properties for application in cropprotection, in particular reduced melting point, reduced lipophilicityand increased water solubility. Such properties have been found to beadvantageous for plant uptake and systemic distribution, see for exampleA. Buchholz, S. Trapp, Pest Manag Sci 2016; 72: 929-939) in order tocontrol certain pest species named below.

Examples of the abovementioned animal pests are:

from the order Acarina, for example,

Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro,Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobiaspp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,Dermatophagoides spp, Eotetranychus spp, Eriophyes spp., Hemitarsonemusspp, Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodoros spp.,Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora,Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalusspp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp,Tarsonemus spp. and Tetranychus spp.;

from the order Anoplura, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. andPhylloxera spp.; from the order Coleoptera, for example,

Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp.,Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis,Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp.,Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp.,Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp.,Heteronychus arator, Hypothenemus hampei, Lagria vilosa, LeptinotarsadecemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp,Maladera castanea, Megascelis spp, Melighetes aeneus, Melolontha spp.,Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophagaspp, PhIyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatusaubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotrogaspp., Somaticus spp, Sphenophorus spp, Sternechus subsignatus, Tenebriospp., Tribolium spp. and Trogoderma spp.; from the order Diptera, forexample,

Aedes spp., Anopheles spp, Antherigona soccata, Bactrocea oleae, Bibiohortulanus, Bradysia spp, Calliphora erythrocephala, Ceratitis spp.,Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp,Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyzatripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyzaspp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp.,Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp.,Rhagoletis spp, Rivelia quadrifasciata, Scatella spp, Sciara spp.,Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;

from the order Hemiptera, for example,

Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus,Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp.,Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma,Dichelops furcatus, Dysdercus spp., Edessa spp, Euschistus spp.,Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horciasnobilellus, Leptocorisa spp., Lygus spp, Margarodes spp, Murgantiahistrionic, Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysiussimulans, Oebalus insularis, Piesma spp., Piezodorus spp, Rhodnius spp.,Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.,Thyanta spp, Triatoma spp., Vatiga illudens;

Acyrthosium pisum, Adalges spp, Agalliana ensigera, Agonoscenatargionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis,Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula,Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotusspp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp,Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariellaaegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalusdictyospermi, Cicadella spp, Cofana spectra, Cryptomyzus spp, Cicadulinaspp, Coccus hesperidum, Dalbulus maidis, Dialeurodes spp, Diaphorinacitri, Diuraphis noxia, Dysaphis spp, Empoasca spp., Eriosoma larigerum,Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphispseudobrassicae, Hyalopterus spp, Hyperomyzus pallidus, Idioscopusclypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni,Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp.,Mahanarva spp, Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus,Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp.,Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter,Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigusspp., Peregrinus maidis, Perkinsiella spp, Phorodon humuli, Phylloxeraspp, Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp.,Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica,Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphumspp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp.,Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina,Toxoptera spp, Trialeurodes spp, Tridiscus sporoboli, Trionymus spp,Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidiascutellaris;

from the order Hymenoptera, for example,

Acromyrmex, Arge spp, Atta spp., Cephus spp., Diprion spp., Diprionidae,Gilpinia polytoma, Hoplo-campa spp., Lasius spp., Monomorium pharaonis,Neodiprion spp., Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp.and Vespa spp.;

from the order Isoptera, for example,

Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermesspp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsisgeminate

from the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabamaargillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrixthurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis,Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysiaambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp,Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis,Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea,Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp, Estigmeneacrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella,Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedyanubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp,Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus,Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostegebifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestrabrassicae, Manduca sexta, Mythimna spp, Noctua spp, Operophtera spp.,Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.,Panolis flammea, Papaipema nebris, Pectinophora gossypiela,Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaeaoperculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp.,Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp.,Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate,Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tutaabsoluta, and Yponomeuta spp.;

from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

from the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscusspp, and Schistocerca spp.;

from the order Psocoptera, for example,

Liposcelis spp.;

from the order Siphonaptera, for example,

Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;

from the order Thysanoptera, for example,

Calliothrips phaseoli, Frankliniella spp., Heliothrips spp,Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii,Sericothrips variabilis, Taeniothrips spp., Thrips spp;

from the order Thysanura, for example, Lepisma saccharina.

The active ingredients according to the invention can be used forcontrolling, i. e. containing or destroying, pests of the abovementionedtype which occur in particular on plants, especially on useful plantsand ornamentals in agriculture, in horticulture and in forests, or onorgans, such as fruits, flowers, foliage, stalks, tubers or roots, ofsuch plants, and in some cases even plant organs which are formed at alater point in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat,barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodderbeet; fruit, for example pomaceous fruit, stone fruit or soft fruit,such as apples, pears, plums, peaches, almonds, cherries or berries, forexample strawberries, raspberries or blackberries; leguminous crops,such as beans, lentils, peas or soya; oil crops, such as oilseed rape,mustard, poppies, olives, sunflowers, coconut, castor, cocoa or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants,such as cotton, flax, hemp orjute; citrus fruit, such as oranges,lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes or bellpeppers; Lauraceae, such as avocado, Cinnamonium or camphor; and alsotobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines,hops, the plantain family and latex plants.

The compositions and/or methods of the present invention may be alsoused on any ornamental and/or vegetable crops, including flowers,shrubs, broad-leaved trees and evergreens.

For example the invention may be used on any of the following ornamentalspecies: Ageratum spp., Alonsoa spp., Anemone spp., Anisodonteacapsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp.(e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp.,Brachycome spp., Brassica spp. (ornamental), Calceolaria spp., Capsicumannuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemumspp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea,Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis,Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp.,Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp.,Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp.,Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp.,Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus,Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesiaspp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp.,Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp.(pansy), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp.,Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp.,Ranunculus spp., Rhododendron spp., Rosa spp. (rose), Rudbeckia spp.,Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthuswisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp.,Nicotinia spp., Verbena spp., Zinnia spp. and other bedding plants.

For example the invention may be used on any of the following vegetablespecies: Allium spp. (A. sativum, A. cepa, A. oschaninii, A. Porrum, A.ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus,Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B.Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichoriumendivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus,Cucumis spp. (C. sativus, C. melo), Cucurbita spp. (C. pepo, C. maxima),Cyanara spp. (C. scolymus, C. cardunculus), Daucus carota, Foeniculumvulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L.esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum,Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisumsativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salviaspp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea,Valerianella spp. (V. locusta, V. eriocarpa) and Vicia faba.

Preferred ornamental species include African violet, Begonia, Dahlia,Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster,Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum,Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia,Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper,tomato and cucumber.

The active ingredients according to the invention are especiallysuitable for controlling Aphis craccivora, Diabrotica balteata,Heliothis virescens, Myzus persicae, Plutella xylostella and Spodopteralittoralis in cotton, vegetable, maize, rice and soya crops. The activeingredients according to the invention are further especially suitablefor controlling Mamestra (preferably in vegetables), Cydia pomonella(preferably in apples), Empoasca (preferably in vegetables, vineyards),Leptinotarsa (preferably in potatos) and Chilo supressalis (preferablyin rice).

The active ingredients according to the invention are especiallysuitable for controlling Aphis craccivora, Diabrotica balteata,Heliothis virescens, Myzus persicae, Plutella xylostella and Spodopteralittoralis in cotton, vegetable, maize, rice and soya crops. The activeingredients according to the invention are further especially suitablefor controlling Mamestra (preferably in vegetables), Cydia pomonella(preferably in apples), Empoasca(preferably in vegetables, vineyards),Leptinotarsa (preferably in potatos) and Chilo supressalis (preferablyin rice).

In a further aspect, the invention may also relate to a method ofcontrolling damage to plant and parts thereof by plant parasiticnematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasiticnematodes), especially plant parasitic nematodes such as root knotnematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogynejavanica, Meloidogyne arenaria and other Meloidogyne species;cyst-forming nematodes, Globodera rostochiensis and other Globoderaspecies; Heterodera avenae, Heterodera glycines, Heterodera schachtii,Heterodera trifolii, and other Heterodera species; Seed gall nematodes,Anguina species; Stem and foliar nematodes, Aphelenchoides species;Sting nematodes, Belonolaimus longicaudatus and other Belonolaimusspecies; Pine nematodes, Bursaphelenchus xylophilus and otherBursaphelenchus species; Ring nematodes, Criconema species, Criconemellaspecies, Criconemoides species, Mesocriconema species; Stem and bulbnematodes, Ditylenchus destructor, Ditylenchus dipsaci and otherDitylenchus species; Awl nematodes, Dolichodorus species; Spiralnematodes, Heliocotylenchus multicinctus and other Helicotylenchusspecies; Sheath and sheathoid nematodes, Hemicycliophora species andHemicriconemoides species; Hirshmanniella species; Lance nematodes,Hoploaimus species; false rootknot nematodes, Nacobbus species; Needlenematodes, Longidorus elongatus and other Longidorus species; Pinnematodes, Pratylenchus species; Lesion nematodes, Pratylenchusneglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchusgoodeyi and other Pratylenchus species; Burrowing nematodes, Radopholussimilis and other Radopholus species; Reniform nematodes, Rotylenchusrobustus, Rotylenchus reniformis and other Rotylenchus species;Scutellonema species; Stubby root nematodes, Trichodorus primitivus andother Trichodorus species, Paratrichodorus species; Stunt nematodes,Tylenchorhynchus claytoni, Tylenchorhynchus dubius and otherTylenchorhynchus species; Citrus nematodes, Tylenchulus species; Daggernematodes, Xiphinema species; and other plant parasitic nematodespecies, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp.,Melinius spp., Punctodera spp., and Quinisulcius spp.

The compounds of the invention may also have activity against themolluscs. Examples of which include, for example, Ampullariidae; Arion(A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae(Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina;Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum);Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H.itala, H. obvia); Helicidae Helicigona arbustorum); Helicodiscus; Helix(H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L.maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M.sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising one or more selectively acting toxins,such as are known, for example, from toxin-producing bacteria,especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popilliae; or insecticidal proteins fromBacillus thuringiensis, such as 8-endotoxins, e.g. Cry1Ab, Cry1Ac,Cry1F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetativeinsecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; orinsecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood by8-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A,Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for exampleVip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncatedtoxins and modified toxins. Hybrid toxins are produced recombinantly bya new combination of different domains of those proteins (see, forexample, WO 2002/15701). Truncated toxins, for example a truncatedCry1Ab, are known. In the case of modified toxins, one or more aminoacids of the naturally occurring toxin are replaced. In such amino acidreplacements, preferably non-naturally present protease recognitionsequences are inserted into the toxin, such as, for example, in the caseof Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3Atoxin (see WO 2003/018810). Examples of such toxins or transgenic plantscapable of synthesising such toxins are disclosed, for example, inEP-A-0 374 753, WO1993/07278, WO1995/34656, EP-A-0 427 529, EP-A-451 878and WO 2003/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. Cryl-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 1990/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGardRootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGardPlus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin);Starlink® (maize variety that expresses a Cry9C toxin); Herculex I®(maize variety that expresses a Cry1 Fa2 toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses aCry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac anda Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and aCry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated Cry1Ab toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a Cry1Ab toxin. Bt176 maize also transgenicallyexpresses the enzyme PAT to achieve tolerance to the herbicideglufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCry3A toxin. This toxin is Cry3A055 modified by insertion of acathepsin-G-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 2003/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a Cry3Bb1 toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.

7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a Cry1Ab toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising antipathogenic substances having aselective action, such as, for example, the so-called“pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).Examples of such antipathogenic substances and transgenic plants capableof synthesising such antipathogenic substances are known, for example,from EP-A-0 392 225, WO 1995/33818 and EP-A-0 353 191. The methods ofproducing such transgenic plants are generally known to the personskilled in the art and are described, for example, in the publicationsmentioned above.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO1995/33818)or protein or polypeptide factors involved in plant pathogen defence(so-called “plant disease resistance genes”, as described in WO2003/000906).

Further areas of use of the compositions according to the invention arethe protection of stored goods and store rooms and the protection of rawmaterials, such as wood, textiles, floor coverings or buildings, andalso in the hygiene sector, especially the protection of humans,domestic animals and productive livestock against pests of the mentionedtype.

The present invention also provides a method for controlling pests (suchas mosquitoes and other disease vectors; see alsohttp://www.who.int/malaria/vector_control/irs/en/). In one embodiment,the method for controlling pests comprises applying the compositions ofthe invention to the target pests, to their locus or to a surface orsubstrate by brushing, rolling, spraying, spreading or dipping. By wayof example, an IRS (indoor residual spraying) application of a surfacesuch as a wall, ceiling or floor surface is contemplated by the methodof the invention. In another embodiment, it is contemplated to applysuch compositions to a substrate such as non-woven or a fabric materialin the form of (or which can be used in the manufacture of) netting,clothing, bedding, curtains and tents.

In one embodiment, the method for controlling such pests comprisesapplying a pesticidally effective amount of the compositions of theinvention to the target pests, to their locus, or to a surface orsubstrate so as to provide effective residual pesticidal activity on thesurface or substrate. Such application may be made by brushing, rolling,spraying, spreading or dipping the pesticidal composition of theinvention. By way of example, an IRS application of a surface such as awall, ceiling or floor surface is contemplated by the method of theinvention so as to provide effective residual pesticidal activity on thesurface. In another embodiment, it is contemplated to apply suchcompositions for residual control of pests on a substrate such as afabric material in the form of (or which can be used in the manufactureof) netting, clothing, bedding, curtains and tents.

Substrates including non-woven, fabrics or netting to be treated may bemade of natural fibres such as cotton, raffia, jute, flax, sisal,hessian, or wool, or synthetic fibres such as polyamide, polyester,polypropylene, polyacrylonitrile or the like. The polyesters areparticularly suitable. The methods of textile treatment are known, e.g.WO 2008/151984, WO 2003/034823, U.S. Pat. No. 5,631,072, WO 2005/64072,WO2006/128870, EP 1724392, WO2005/113886 or WO 2007/090739.

Further areas of use of the compositions according to the invention arethe field of tree injection/trunk treatment for all ornamental trees aswell all sort of fruit and nut trees.

In the field of tree injection/trunk treatment, the compounds accordingto the present invention are especially suitable against wood-boringinsects from the order Lepidoptera as mentioned above and from the orderColeoptera, especially against woodborers listed in the following tablesA and B:

TABLE A Examples of exotic woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus planipennis AshCerambycidae Anoplura glabripennis Hardwoods Scolytidae Xylosandruscrassiusculus Hardwoods X. mutilatus Hardwoods Tomicus piniperdaConifers

TABLE B Examples of native woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus anxius Birch Agriluspolitus Willow, Maple Agrilus sayi Bayberry, Sweetfern Agrilusvittaticolllis Apple, Pear, Cranberry, Serviceberry, HawthornChrysobothris femorata Apple, Apricot, Beech, Boxelder, Cherry,Chestnut, Currant, Elm, Hawthorn, Hackberry, Hickory, Horsechestnut,Linden, Maple, Mountain-ash, Oak, Pecan, Pear, Peach, Persimmon, Plum,Poplar, Quince, Redbud, Serviceberry, Sycamore, Walnut, Willow Texaniacampestris Basswood, Beech, Maple, Oak, Sycamore, Willow, Yellow-poplarCerambycidae Goes pulverulentus Beech, Elm, Nuttall, Willow, Black oak,Cherrybark oak, Water oak, Sycamore Goes tigrinus Oak Neoclytusacuminatus Ash, Hickory, Oak, Walnut, Birch, Beech, Maple, Easternhophornbeam, Dogwood, Persimmon, Redbud, Holly, Hackberry, Black locust,Honeylocust, Yellow-poplar, Chestnut, Osage-orange, Sassafras, Lilac,Mountain-mahogany, Pear, Cherry, Plum, Peach, Apple, Elm, Basswood,Sweetgum Neoptychodes trilineatus Fig, Alder, Mulberry, Willow, Netleafhackberry Oberea ocellata Sumac, Apple, Peach, Plum, Pear, Currant,Blackberry Oberea tripunctata Dogwood, Viburnum, Elm, Sourwood,Blueberry, Rhododendron, Azalea, Laurel, Poplar, Willow, MulberryOncideres cingulata Hickory, Pecan, Persimmon, Elm, Sourwood, Basswood,Honeylocust, Dogwood, Eucalyptus, Oak, Hackberry, Maple, Fruit treesSaperda calcarata Poplar Strophiona nitens Chestnut, Oak, Hickory,Walnut, Beech, Maple Scolytidae Corthylus columbianus Maple, Oak,Yellow-poplar, Beech, Boxelder, Sycamore, Birch, Basswood, Chestnut, ElmDendroctonus frontalis Pine Dryocoetes betulae Birch, Sweetgum, Wildcherry, Beech, Pear Monarthrum fasciatum Oak, Maple, Birch, Chestnut,Sweetgum, Blackgum, Poplar, Hickory, Mimosa, Apple, Peach, PinePhloeotribus liminaris Peach, Cherry, Plum, Black cherry, Elm, Mulberry,Mountain-ash Pseudopityophthorus pruinosus Oak, American beech, Blackcherry, Chickasaw plum, Chestnut, Maple, Hickory, Hornbeam, HophornbeamSesiidae Paranthrene simulans Oak, American chestnut Sanninauroceriformis Persimmon Synanthedon exitiosa Peach, Plum, Nectarine,Cherry, Apricot, Almond, Black cherry Synanthedon pictipes Peach, Plum,Cherry, Beach, Black Cherry Synanthedon rubrofascia Tupelo Synanthedonscitula Dogwood, Pecan, Hickory, Oak, Chestnut, Beech, Birch, Blackcherry, Elm, Mountain-ash, Viburnum, Willow, Apple, Loquat, Ninebark,Bayberry Vitacea polistiformis Grape

The present invention may be also used to control any insect pests thatmay be present in turfgrass, including for example beetles,caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites,mole crickets, scales, mealybugs ticks, spittlebugs, southern chinchbugs and white grubs. The present invention may be used to controlinsect pests at various stages of their life cycle, including eggs,larvae, nymphs and adults.

In particular, the present invention may be used to control insect peststhat feed on the roots of turfgrass including white grubs (such asCyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp.(e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green Junebeetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica),Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Blackturfgrass ataenius, A. spretulus), Maladera spp. (e.g. Asiatic gardenbeetle, M. castanea) and Tomarus spp.), ground pearls (Margarodes spp.),mole crickets (tawny, southern, and short-winged; Scapteriscus spp.,Gryllotalpa africana) and leatherjackets (European crane fly, Tipulaspp.).

The present invention may also be used to control insect pests ofturfgrass that are thatch dwelling, including armyworms (such as fallarmyworm Spodoptera frugiperda, and common armyworm Pseudaletiaunipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatusverstitus and S. parvulus), and sod webworms (such as Crambus spp. andthe tropical sod webworm, Herpetogramma phaeopteralis).

The present invention may also be used to control insect pests ofturfgrass that live above the ground and feed on the turfgrass leaves,including chinch bugs (such as southern chinch bugs, Blissus insularis),Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug(Antonina graminis), two-lined spittlebug (Propsapia bicincta),leafhoppers, cutworms (Noctuidae family), and greenbugs.

The present invention may also be used to control other pests ofturfgrass such as red imported fire ants (Solenopsis invicta) thatcreate ant mounds in turf.

In the hygiene sector, the compositions according to the invention areactive against ectoparasites such as hard ticks, soft ticks, mangemites, harvest mites, flies (biting and licking), parasitic fly larvae,lice, hair lice, bird lice and fleas.

Examples of such parasites are:

Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculusspp. and Phtirus spp., Solenopotes spp.

Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

Of the order Diptera and the suborders Nematocerina and Brachycerina,for example Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

Of the order Siphonapterida, for example Pulex spp., Ctenocephalidesspp., Xenopsylla spp., Ceratophyllus spp.

Of the order Heteropterida, for example Cimex spp., Triatoma spp.,Rhodnius spp., Panstrongylus spp.

Of the order Blattarida, for example Blatta orientalis, Periplanetaamericana, Blattelagermanica and Supella spp.

Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata,for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,Pneumonyssus spp., Sternostoma spp. and Varroa spp.

Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), forexample Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobiaspp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp.,Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp.,Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. andLaminosioptes spp.

The compositions according to the invention are also suitable forprotecting against insect infestation in the case of materials such aswood, textiles, plastics, adhesives, glues, paints, paper and card,leather, floor coverings and buildings.

The compositions according to the invention can be used, for example,against the following pests: beetles such as Hylotrupes bajulus,Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum,Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobiumcarpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctuslinearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis,Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychuscapucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderusminutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas,Urocerus gigas taignus and Urocerus augur, and termites such asKalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus, and bristletails such as Lepisma saccharina.

The compounds according to the invention can be used as pesticidalagents in unmodified form, but they are generally formulated intocompositions in various ways using formulation adjuvants, such ascarriers, solvents and surface-active substances. The formulations canbe in various physical forms, e.g. in the form of dusting powders, gels,wettable powders, water-dispersible granules, water-dispersible tablets,effervescent pellets, emulsifiable concentrates, microemulsifiableconcentrates, oil-in-water emulsions, oil-flowables, aqueousdispersions, oily dispersions, suspo-emulsions, capsule suspensions,emulsifiable granules, soluble liquids, water-soluble concentrates (withwater or a water-miscible organic solvent as carrier), impregnatedpolymer films or in other forms known e.g. from the Manual onDevelopment and Use of FAO and WHO Specifications for Pesticides, UnitedNations, First Edition, Second Revision (2010). Such formulations caneither be used directly or diluted prior to use. The dilutions can bemade, for example, with water, liquid fertilisers, micronutrients,biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredientwith the formulation adjuvants in order to obtain compositions in theform of finely divided solids, granules, solutions, dispersions oremulsions. The active ingredients can also be formulated with otheradjuvants, such as finely divided solids, mineral oils, oils ofvegetable or animal origin, modified oils of vegetable or animal origin,organic solvents, water, surface-active substances or combinationsthereof.

The active ingredients can also be contained in very fine microcapsules.Microcapsules contain the active ingredients in a porous carrier. Thisenables the active ingredients to be released into the environment incontrolled amounts (e.g. slow-release). Microcapsules usually have adiameter of from 0.1 to 500 microns. They contain active ingredients inan amount of about from 25 to 95% by weight of the capsule weight. Theactive ingredients can be in the form of a monolithic solid, in the formof fine particles in solid or liquid dispersion or in the form of asuitable solution. The encapsulating membranes can comprise, forexample, natural or synthetic rubbers, cellulose, styrene/butadienecopolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides,polyureas, polyurethane or chemically modified polymers and starchxanthates or other polymers that are known to the person skilled in theart. Alternatively, very fine microcapsules can be formed in which theactive ingredient is contained in the form of finely divided particlesin a solid matrix of base substance, but the microcapsules are notthemselves encapsulated.

The formulation adjuvants that are suitable for the preparation of thecompositions according to the invention are known per se. As liquidcarriers there may be used: water, toluene, xylene, petroleum ether,vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acidanhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone,butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkylesters of acetic acid, diacetone alcohol, 1,2-dichloropropane,diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycolabietate, diethylene glycol butyl ether, diethylene glycol ethyl ether,diethylene glycol methyl ether, N,N-dimethylformamide, dimethylsulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methylether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone,ethyl acetate, 2-ethylhexanol, ethylene carbonate,1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyllactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycolmethyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glyceroldiacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamylacetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene,isopropyl myristate, lactic acid, laurylamine, mesityl oxide,methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyllaurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene,n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleicacid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid,propyl lactate, propylene carbonate, propylene glycol, propylene glycolmethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol,xylenesulfonic acid, paraffin, mineral oil, trichloroethylene,perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propyleneglycol methyl ether, diethylene glycol methyl ether, methanol, ethanol,isopropanol, and alcohols of higher molecular weight, such as amylalcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol,propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like.

Suitable solid carriers are, for example, talc, titanium dioxide,pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone,calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks,wheat flour, soybean flour, pumice, wood flour, ground walnut shells,lignin and similar substances.

A large number of surface-active substances can advantageously be usedin both solid and liquid formulations, especially in those formulationswhich can be diluted with a carrier prior to use. Surface-activesubstances may be anionic, cationic, non-ionic or polymeric and they canbe used as emulsifiers, wetting agents or suspending agents or for otherpurposes. Typical surface-active substances include, for example, saltsof alkyl sulfates, such as diethanolammonium lauryl sulfate; salts ofalkylarylsulfonates, such as calcium dodecylbenzenesulfonate;alkylphenol/alkylene oxide addition products, such as nonylphenolethoxylate; alcohol/alkylene oxide addition products, such astridecylalcohol ethoxylate; soaps, such as sodium stearate; salts ofalkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate;dialkyl esters of sulfosuccinate salts, such as sodiumdi(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitololeate; quaternary amines, such as lauryltrimethylammonium chloride,polyethylene glycol esters of fatty acids, such as polyethylene glycolstearate; block copolymers of ethylene oxide and propylene oxide; andsalts of mono- and di-alkylphosphate esters; and also further substancesdescribed e.g. in McCutcheon's Detergents and Emulsifiers Annual, MCPublishing Corp., Ridgewood N.J. (1981).

Further adjuvants that can be used in pesticidal formulations includecrystallisation inhibitors, viscosity modifiers, suspending agents,dyes, anti-oxidants, foaming agents, light absorbers, mixingauxiliaries, antifoams, complexing agents, neutralising or pH-modifyingsubstances and buffers, corrosion inhibitors, fragrances, wettingagents, take-up enhancers, micronutrients, plasticisers, glidants,lubricants, dispersants, thickeners, antifreezes, microbicides, andliquid and solid fertilisers.

The compositions according to the invention can include an additivecomprising an oil of vegetable or animal origin, a mineral oil, alkylesters of such oils or mixtures of such oils and oil derivatives. Theamount of oil additive in the composition according to the invention isgenerally from 0.01 to 10%, based on the mixture to be applied. Forexample, the oil additive can be added to a spray tank in the desiredconcentration after a spray mixture has been prepared. Preferred oiladditives comprise mineral oils or an oil of vegetable origin, forexample rapeseed oil, olive oil or sunflower oil, emulsified vegetableoil, alkyl esters of oils of vegetable origin, for example the methylderivatives, or an oil of animal origin, such as fish oil or beeftallow. Preferred oil additives comprise alkyl esters of C₈-C₂₂ fattyacids, especially the methyl derivatives of C₁₂-C₁₈ fatty acids, forexample the methyl esters of lauric acid, palmitic acid and oleic acid(methyl laurate, methyl palmitate and methyl oleate, respectively). Manyoil derivatives are known from the Compendium of Herbicide Adjuvants,10^(th) Edition, Southern Illinois University, 2010.

The inventive compositions generally comprise from 0.1 to 99% by weight,especially from 0.1 to 95% by weight, of compounds of the presentinvention and from 1 to 99.9% by weight of a formulation adjuvant whichpreferably includes from 0 to 25% by weight of a surface-activesubstance. Whereas commercial products may preferably be formulated asconcentrates, the end user will normally employ dilute formulations.

The rates of application vary within wide limits and depend on thenature of the soil, the method of application, the crop plant, the pestto be controlled, the prevailing climatic conditions, and other factorsgoverned by the method of application, the time of application and thetarget crop. As a general guideline compounds may be applied at a rateof from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.

Preferred formulations can have the following compositions (weight %):

Emulsifiable Concentrates:

active ingredient: 1 to 95%, preferably 60 to 90%

surface-active agent: 1 to 30%, preferably 5 to 20%

liquid carrier: 1 to 80%, preferably 1 to 35%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 5%

solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50%

water: 94 to 24%, preferably 88 to 30%

surface-active agent: 1 to 40%, preferably 2 to 30%

Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80%

surface-active agent: 0.5 to 20%, preferably 1 to 15%

solid carrier: 5 to 95%, preferably 15 to 90%

Granules:

active ingredient: 0.1 to 30%, preferably 0.1 to 15%

solid carrier: 99.5 to 70%, preferably 97 to 85%

The following Examples further illustrate, but do not limit, theinvention.

Wettable powders a) b) c) active ingredients 25% 50% 75% sodiumlignosulfonate  5%  5% — sodium lauryl sulfate  3% —  5% sodiumdiisobutylnaphthalenesulfonate —  6% 10% phenol polyethylene glycolether —  2% — (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27% —

The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording wettable powders thatcan be diluted with water to give suspensions of the desiredconcentration.

Powders for dry seed treatment a) b) c) active ingredients 25% 50% 75%light mineral oil  5%  5%  5% highly dispersed silicic acid  5%  5% —Kaolin 65% 40% — Talcum — 20%

The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording powders that can beused directly for seed treatment.

Emulsifiable concentrate active ingredients 10% octylphenol polyethyleneglycol ether  3% (4-5 mol of ethylene oxide) calciumdodecylbenzenesulfonate  3% castor oil polyglycol ether  4% (35 mol ofethylene oxide) Cyclohexanone 30% xylene mixture 50%

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dusts a) b) c) Active ingredients  5%  6% 4% Talcum 95% — — Kaolin — 94%— mineral filler — — 96%

Ready-for-use dusts are obtained by mixing the combination with thecarrier and grinding the mixture in a suitable mill. Such powders canalso be used for dry dressings for seed.

Extruder granules Active ingredients 15% sodium lignosulfonate  2%carboxymethylcellulose  1% Kaolin 82%

The combination is mixed and ground with the adjuvants, and the mixtureis moistened with water.

The mixture is extruded and then dried in a stream of air.

Coated granules Active ingredients 8% polyethylene glycol (mol. wt. 200)3% Kaolin 89%

The finely ground combination is uniformly applied, in a mixer, to thekaolin moistened with polyethylene glycol. Non-dusty coated granules areobtained in this manner.

Suspension Concentrate

active ingredients 40% propylene glycol 10% nonylphenol polyethyleneglycol ether  6% (15 mol of ethylene oxide) Sodium lignosulfonate 10%carboxymethylcellulose  1% silicone oil (in the form of a 75 %  1%emulsion in water) Water 32%

The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

Flowable Concentrate for Seed Treatment

active ingredients 40% propylene glycol  5% copolymer butanol PO/EO  2%Tristyrenephenole with 10-20 moles EO  2% 1,2-benzisothiazolin-3-one (inthe form 0.5%  of a 20% solution in water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% 0.2%  emulsion in water) Water45.3% 

The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

Slow Release Capsule Suspension

28 parts of the combination are mixed with 2 parts of an aromaticsolvent and 7 parts of toluenediisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). Thismixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol,0.05 parts of a defoamer and 51.6 parts of water until the desiredparticle size is achieved. To this emulsion a mixture of 2.8 parts1,6-diaminohexane in 5.3 parts of water is added. The mixture isagitated until the polymerization reaction is completed. The obtainedcapsule suspension is stabilized by adding 0.25 parts of a thickener and3 parts of a dispersing agent. The capsule suspension formulationcontains 28% of the active ingredients. The medium capsule diameter is8-15 microns. The resulting formulation is applied to seeds as anaqueous suspension in an apparatus suitable for that purpose.

Formulation types include an emulsion concentrate (EC), a suspensionconcentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), awater dispersible granule (WG), an emulsifiable granule (EG), anemulsion, water in oil (EO), an emulsion, oil in water (EW), amicro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable(OF), an oil miscible liquid (OL), a soluble concentrate (SL), anultra-low volume suspension (SU), an ultra-low volume liquid (UL), atechnical concentrate (TK), a dispersible concentrate (DC), a wettablepowder (WP), a soluble granule (SG) or any technically feasibleformulation in combination with agriculturally acceptable adjuvants.

PREPARATORY EXAMPLES

“Mp” means melting point in ° C. Free radicals represent methyl groups.¹H NMR measurements were recorded on a Brucker 400 MHz spectrometer,chemical shifts are given in ppm relevant to a TMS standard. Spectrameasured in deuterated solvents as indicated. Either one of the LCMSmethods below was used to characterize the compounds. The characteristicLCMS values obtained for each compound were the retention time (“Rt”,recorded in minutes) and the measured molecular ion (M+H)⁺ or (M−H)−.

LCMS and GCMS Methods:

Method 1:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDIISingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive and negative ions, Capillary: 3.00 kV, Conerange: 30 V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 50 I/h, Desolvation Gas Flow: 650I/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment, diode-array detector and ELSD detector.Column: Waters UPLC HSS T3, 1.8 □m, 30×2.1 mm, Temp: 60° C., DADWavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 1.2min; Flow (ml/min) 0.85

Method 2:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDIISingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive and negative ions), Capillary: 3.00 kV, Conerange: 30V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 50 I/h, Desolvation Gas Flow: 650I/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment, diode-array detector and ELSD detector.Column: Waters UPLC HSS T3, 1.8 □m, 30×2.1 mm, Temp: 60° C., DADWavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 2.7min; Flow (ml/min) 0.85

Method 3:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII orZQ Single quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive and negative ions), Capillary: 3.00 kV, Conerange: 30 V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 50 I/h, Desolvation Gas Flow: 650I/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment, diode-array detector and ELSD detector.Column: Waters UPLC HSS T3, 1.8 □m, 30×2.1 mm, Temp: 60° C., DADWavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 0-10% B in 2.5min; Flow (ml/min) 0.85

Method 4:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDIISingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive and negative ions), Capillary: 3.00 kV, Conerange: 30 V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650I/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment, diode-array detector and ELSD detector.Column: Waters UPLC HSS T3, 1.8 □m, 30×2.1 mm, Temp: 60° C., DADWavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 40-100% B in 1.2min; Flow (ml/min) 0.85

Method 5:

Spectra were recorded on a Mass Spectrometer from Waters (Acquity SDSMass Spectrometer) equipped with an electrospray source (Polarity:Positive and Negative Polarity Switch, Capillary: 3.00 kV, Cone Voltage:41.00 V, Source temperature: 150° C., Desolvation Gas Flow: 1000 L/Hr.,Desolvation temperature: 500° C., Gas Flow @Cone: 50 L/hr., Mass range:110-800 Da, PDA wavelength range: 210-400 nm. Column: Acquity UPLC HSST3 C18, length 30 mm, diameter 2.1 mm, particle size 1.8 μm. Column oventemperature 40° C. Solvent gradient: A=Water with 0.1% formicacid:Acetonitrile (95:5 v/v). B=Acetonitrile with 0.05% formic acid.Gradient=0 min 90% A, 10% B; 0.2 min 50% A, 50% B; 0.7-1.3 min 0% A,100% B; 1.4-1.6 min 90% A, 10% B. Flow rate 0.6 mL/min.

Example H1: Preparation of1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile(Table P, Example P10)

Step 1: Preparation of methyl5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylate

Methyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate, prepared asdescribed in patent WO 2017/089190 (32 g, 115.88 mmol) was dissolved indimethyl sulfoxide (350 mL). Then ethyl 2-cyanoacetate (18.5 mL, 173.82mmol), potassium carbonate (40.442 g, 289.70 mmol) andtetrabutylammonium bromide (3.81 g, 11.588 mmol) were added successivelyat room temperature. The resulting suspension were stirred one night at90° C. and then cooled to room temperature. Water and ethyl acetate wereadded, the resulting mixture was cooled down at 0° C. and hydrochloricacid (2M) was added slowly to acidify the reaction to pH 4-5. Theaqueous layer was extracted with ethyl acetate three times. The combinedorganic layers were, dried over sodium sulfate, filtered andconcentrated in vacuo. The crude obtained was heated at 80° C. inethanol (250 ml) for 1 hour. The solution obtained was cooled to 0° C.,stirred 1 hour and filtered. The precipitate was washed with coldethanol to afford methyl5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylate.

LCMS (method 1): 309 (M+H)⁺; retention time: 0.85 min.

1H NMR (400 MHz, CHLOROFORM-D) δ ppm 1.33 (t, J=7.15 Hz, 3H) 1.45 (t,J=7.34 Hz, 3H) 2.98-3.05 (m, 2H) 4.04 (s, 3H) 4.28-4.35 (m, 2H) 4.84 (s,1H) 7.83 (d, J=1.83 Hz, 1H) 8.49 (d, J=1.83 Hz, 1H).

Step 2: Preparation of methyl5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carboxylate

Methyl 5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanyl-pyridine-2-(7.3g, 24 mmol) was dissolved in dimethylsulfoxide (70 mL). To this wasadded NaCl (14 g, 240 mmol) and water (35 mL) successively at roomtemperature. The resulting suspension was stirred for 3 hours at 125° C.The reaction mixture was cooled to room temperature, diluted with 50 mLof water and 100 mL of ethyl acetate. The aqueous layer was extractedwith ethyl acetate three times. The organic layers were combined, driedover sodium sulfate and concentrated in vacuo. The crude product waspurified over silica gel to afford methyl5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carboxylate.

LCMS (method 1): 237 (M+H)⁺; retention time: 0.72 min.

1H NMR (400 MHz, CHLOROFORM-D) δ ppm 1.45 (t, J=7.52 Hz, 3H) 3.01 (q,J=7.34 Hz, 2H) 3.87 (s, 2H) 4.04 (s, 3H) 7.72 (d, J=1.83 Hz, 1H)8.35-8.41 (m, 1H).

Step 3: Preparation of methyl5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylate

Methyl 5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carboxylate (5 g,21.16 mmol) was dissolved in acetonitrile (170 mL) and treated withcesium carbonate (20.7 g, 63.48 mmol) and 1,2-dibromoethane (2.19 mL,25.39 mmol) at room temperature. The resulting mixture was stirred 3h 30hours at 80° C. and then at room temperature overnight. The reactionmixture was diluted with water and ethyl acetate. The aqueous layer wasextracted 3 times with ethyl acetate. The combined organic layers werewashed with brine, dried over sodium sulfate, filtered and concentratedin vacuo to afford the crude product which was purified bychromatography to afford methyl5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylate.

LCMS (method 1): 263 (M+H)⁺; retention time: 0.85 min.

1H NMR (400 MHz, CHLOROFORM-D) δ ppm 1.45 (t, J=7.34 Hz, 3H) 1.54-1.62(m, 2H) 1.89-1.96 (m, 2H) 3.01 (q, J=7.34 Hz, 2H) 4.02 (s, 3H) 7.74 (d,J=2.20 Hz, 1H) 8.17 (d, J=1.83 Hz, 1H).

Step 4: Preparation of5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid

Methyl 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylate(2.63 g, 10.0 mmol) was dissolved in tetrahydrofurane (50 mL) and water(15 mL). Then lithium hydroxide (0.375 g, 15.0 mmol) was added andreaction was stirred one night at rt. After this time, a further portionof lithium hydroxide (0.160 g, 7.0 mmol) was added and the reaction wasstirred for a further 2 hours at RT. The reaction mixture wasconcentrated in vacuo and the residue was dissolved in dichloromethane.Aqueous HCl 1 M was added and the aqueous layer (pH 1) was extracted 3times with dichloromethane. The combined organic layers were dried oversodium sulfate, filtered and concentrated in vacuo to afford5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid.

LCMS (method 1): 249 (M+H)⁺; retention time: 0.67 min.

1H NMR (400 MHz, DMSO-d Solvent) δ ppm 1.26 (t, J=7.34 Hz, 3H) 1.70-1.78(m, 2H) 1.83-1.92 (m, 2H) 3.03 (q, J=7.34 Hz, 2H) 7.63 (d, J=2.20 Hz,1H) 8.37 (d, J=1.83 Hz, 1H) 13.16-13.40 (m, 1H).

Step 5. Preparation of5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[3-(methylamino)-6-(trifluoromethyl)pyridazin-4-yl]pyridine-2-carboxamide

5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (200mg, 0.8055 mmol) was dissolved in dichloromethane (10 mL) andN,N-dimethylformamide (10.0 μL) was added. In this suspension, oxalyldichloride (0.118 mL, 1.369 mmol,) was added dropwise via syringe. Theresulting yellowish suspension was stirred at room temperature. After1.5h, reaction mixture was concentrated in vacuo to afford5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonyl chloride. Thefresh 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonylchloride (250 mg, 0.9370 mmol) was dissolved in tetrahydrofurane (12 mL)and N,N-diethylethanamine (0.27 mL, 1.933 mmol) was added dropwiseN3-methyl-6-(trifluoromethyl)pyridazine-3,4-diamine (651 mg, 3.222 mmol)in tetrahydrofurane (12 mL) was then added at 0° C. The resultingmixture was stirred at room temperature for 12 hours. The reactionmixture was then poured into water (20 ml) and extracted withdichloromethane (3×20 ml). The combined extracts were washed with brine(30 ml), dried with sodium sulfate, filtered and concentrated in vacuo.The crude product was purified by chromatography over silica gel toaffordN-[4-amino-6-(trifluoromethyl)pyridazin-3-yl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide

LCMS (method 2): retention time: 1.04 min, 423 (M+H)⁺.

Step 6: Preparation of1-[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile

5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[3-(methylamino)-6-(trifluoromethyl)pyridazin-4-yl]pyridine-2-carboxamide(240 mg, 0.5682 mmol) and glacial acetic acid (3 mL) were mixed andstirred one night at reflux and then cooled to room temperature. Aceticacid was removed under reduced pressure and the residue obtained wasdissolved in ethyl acetate, and basified using aqueousbicarbonate-solution. The aqueous layer was extracted with ethyl acetate(3×20 ml) and the combined organic layer were dried with sodium sulfate,filtered and concentrated in vacuo. The crude product was purified bychromatography over silica gel to afford1-[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile.

LCMS (method 2): retention time: 1.05 min, (M+H)⁺ 405.

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.34-1.46 (m, 1H) 1.38 (s, 2H)1.62-1.66 (m, 2H) 1.89-2.02 (m, 2H) 2.97-3.10 (m, 2H) 4.26 (s, 3H)7.76-7.84 (m, 1H) 8.22-8.27 (m, 1H) 8.34-8.41 (m, 1H).

Step 7: Preparation of1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile(Table P, Example P10)

1-[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile(120 mg, 0.2967 mmol) was dissolved in methanol (6 mL). Then ammoniumcarbamate (46 mg, 0.5935 mmol) and (diacetoxyiodo)benzene (243 mg,0.7418 mmol) were added at room temperature. The suspension obtainedbecame a solution after a few minutes and was stirred for 2 hours atroom temperature. The reaction mixture was quenched with water (20 ml)and extracted with dichloromethane (3×20 ml). The combined organiclayers were washed with brine (30 ml), dried with anhydrous sodiumsulphate, filtered and concentrated in vacuo. The residue was purifiedby chromatography over silica gel using methanol and dichloromethane toafford the1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile.

LCMS (method 2): retention time: 0.85 min, 436.36 (M+H)⁺.

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.14-1.32 (m, 3H) 1.25-1.32 (m, 2H)1.37-1.44 (m, 3H) 1.67-1.77 (m, 2H) 2.03-2.12 (m, 1H) 2.06-2.10 (m, 1H)2.11 (br dd, J=3.48, 2.38 Hz, 1H) 2.68-2.84 (m, 1H) 3.71-3.81 (m, 1H)3.84-3.94 (m, 1H) 4.00-4.14 (m, 3H) 8.18 (s, 1H) 8.36 (d, J=2.20 Hz, 1H)9.04 (d, J=2.20 Hz, 1H)

Example H2. Preparation of1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile(Example P6, Table P)

Step 1: Preparation of5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]pyridine-2-carboxamide

5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (2.4g, 9.7 mmol) was dissolved in dichloromethane (100 mL).N,N-dimethylformamide (10.0 μL) was added followed by the addition ofoxalyl dichloride (1 mL, 12 mmol) dropwise via syringe. The resultingyellowish suspension was stirred at room temperature for 1 hour then thesolvent was concentrated in vacuo. The resulting solid was dissolved intetrahydrofurane (30 ml) and added to a solution ofN2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (1.8 g, 9.7 mmol) andN,N-diethylethanamine (3.3 mL, 23 mmol) in tetrahydrofurane (75 mL) at0° C. The resulting mixture was stirred 30′ at 0° C. then 2 hours atroom temperature. The reaction mixture was treated with NH₄Cl sat soland diluted with ethyl acetate. The aqueous layer was extracted 3 timeswith ethyl acetate. The combined organic layers were washed with brine,dried over Na₂SO₄, filtered and concentrated in vacuo to afford5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]pyridine-2-carboxamideas crude which was used in the next step without further purification.

LCMS (method 1): 422 (M+H)⁺; retention time: 1.03 min.

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.48 (t, J=7.34 Hz, 3H) 1.58-1.63(m, 2H) 1.93-1.99 (m, 2H) 3.01 (q, J=7.34 Hz, 2H) 3.09 (d, J=4.77 Hz,3H) 5.02 (br d, J=4.03 Hz, 1H) 7.71 (d, J=2.20 Hz, 1H) 7.94 (d, J=2.20Hz, 1H) 8.16 (d, J=2.20 Hz, 1H) 8.36 (d, J=0.73 Hz, 1H) 9.53-9.60 (m,1H).

Step 2: Preparation of1-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile

5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]pyridine-2-carboxamide(4.2 g, 10 mmol) was dissolved in acetic acid (100 mL) and the resultingsolution was stirred 18 hours at 110° C. Acetic acid was removed by invacuo and the crude product was purified by chromatography over silicagel to afford1-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile,Mp 142-144° C.

LCMS (method 1): 404 (M+H)⁺; retention time: 1.07 min.

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.40 (t, J=7.34 Hz, 3H) 1.59-1.64(m, 2H) 1.90-1.97 (m, 2H) 3.03 (q, J=7.46 Hz, 2H) 4.07 (s, 3H) 7.77 (d,J=2.20 Hz, 1H) 8.35 (d, J=2.20 Hz, 1H) 8.42 (d, J=1.47 Hz, 1H) 8.73-8.78(m, 1H).

Step 3: Preparation of1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile((Example P6, Table P)

Sulfoximine formation analogous to Example H1, Step 7.

LCMS (method 1): 435 (M+H)⁺; retention time: 0.87 min.

¹H NMR (400 MHz, Chloroform) δ ppm 1.44 (t, J=7.34 Hz, 3H) 1.75-1.80 (m,2H) 2.02-2.08 (m, 2H) 3.94 (s, 3H) 3.94-4.26 (m, 2H) 8.33 (d, J=1.47 Hz,1H) 8.39 (d, J=2.20 Hz, 1H) 8.79 (d, J=1.47 Hz, 1H) 9.06-9.09 (m, 1H).

Example H3: Preparation of1-[5-(ethylsulfonimidoyl)-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile(Example P8, Table P)

Step 1: Preparation ofN-[4-bromo-6-(difluoromethyl)-1-methoxy-2-oxo-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide

To a solution of4-bromo-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (5.0g, 16.61 mmol) in dichloromethane (100 mL) was added trifluoroaceticanhydride (7.09 mL, 49.82 mmol) at room temperature. The reactionmixture was stirred for 30 minutes at room temperature and thenconcentrated in vacuo. Water (100 mL), then an aqueous saturatedpotassium carbonate solution (50 mL) were added and the aqueous layerwas extracted with ethyl acetate (100 mL). The organic layer was washedwith brine (100 mL), dried over sodium sulfate, filtered andconcentrated in vacuo. The crude product was purified over silica gel toafford pureN-[4-bromo-6-(difluoromethyl)-1-methoxy-2-oxo-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide.

This material was used in the next step without further purification.

LCMS (method 5): 397/399 (M+H)⁺, retention time 0.96 min. ¹H NMR (400MHz, CDCl3) δ ppm 3.27 (s, 3H), 4.16 (s, 3H), 6.84 (s, 1H).

Step 2: Preparation ofN-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide

To a solution ofN-[4-bromo-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide(11.8 g, 29.7 mmol) in N,N-dimethylformamide (110 mL) was added sodiumazide (2.9 g, 44.6 mmol) at room temperature. The reaction mixture wasstirred at room temperature overnight. The above reaction was separatelyduplicated, then the combined reaction mixtures were diluted with coldwater (500 mL) and extracted with ethyl acetate (3×150 mL). The combinedorganic layers were washed with water (100 mL) and brine, dried oversodium sulfate, filtered and concentrated in vacuo below 40° C. toaffordN-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide.This material was used in the next step without further purification.

LCMS (method 5): 360 (M+H)⁺, retention time 0.90 min. ¹H NMR (400 MHz,CDCl3) δ ppm 3.23 (s, 3H), 4.15 (s, 3H), 6.40 (s, 1H).

Step 3: Preparation of4-azido-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one

To a solution ofN-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide(4.6 g, 13.0 mmol) in methanol (100 mL) was added potassium carbonate(4.7 g, 33.0 mmol). The reaction mixture was stirred at room temperatureovernight, then diluted with water (150 mL). The aqueous layer wasextracted with ethyl acetate (2×75 mL), the combined organic layerswashed with brine (150 mL), dried over sodium sulfate, filtered andconcentrated in vacuo. The crude product was purified on silica gel (40%ethyl acetate in cyclohexane) to afford4-azido-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (2.2g, 8.4 mmol).

LCMS (method E): 264 (M+H)⁺, retention time 0.94 min. ¹H NMR (400 MHz,CDCl3) δ ppm 3.18 (s, 3H), 4.11 (s, 3H), 6.46 (s, 1H).

Step 4: Preparation of4-amino-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one

To a solution of4-azido-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (1.7g, 6.5 mmol) in tetrahydrofurane (50 mL) and water (5 mL) at roomtemperature was added triphenylphosphine (5.1 g, 19 mmol) and theresulting mixture stirred at room temperature for 2 hours. A 2M aqueoushydrochloric acid solution (9 mL, 18 mmol, 2 mol/L) was added andstirring continued overnight at room temperature. The reaction mixturewas concentrated and quenched using an aqueous saturated potassiumcarbonate solution (20 mL). The aqueous layer was extracted with ethylacetate (2×75 mL), the combined organic layers washed with brine (100mL), dried over sodium sulfate, filtered and concentrated in vacuo. Theresidue was purified on silica gel (50-60% ethyl acetate in cyclohexane)to afford4-amino-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one.

LCMS (method 5): 238 (M+H)⁺, retention time 0.18 min. ¹H NMR (400 MHz,d6-DMSO) δ ppm 2.60 (s, 3H), 3.98 (s, 3H), 5.75 (s, 2H), 6.42 (s, 1H).

Step 5: Preparation of5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamideandN-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide(isomeric mixture)

To a suspension of5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (400mg, 1.61 mmol) in dichloromethane (16 mL) were added a catalytic amountof N,N-dimethylformamide (2 drops) and oxalyl chloride (3.22 mmol, 0.287mL) dropwise. The reaction was stirred at room temperature for 6 hoursand the solvent was removed in vacuo to afford5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonyl chloride.

A solution of above5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonyl chloride (428mg, 1.60 mmol) in dry tetrahydrofurane (20 mL) was added slowly to amixture of4-amino-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one(456.6 mg, 1.92 mmol) and triethylamine (0.678 mL, 4.81 mmol) intetrahydrofurane (9.6 mL). The reaction mixture was stirred at roomtemperature for 2 hours, then quenched with water and extracted withdichloromethane (100 ml). The combined organic layers were washed withwater and brine, dried with anhydrous sodium sulfate and concentrated invacuo to afford the desired isomeric mixture of5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamideandN-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide(750 mg, 1.60 mmol). This material was used in the next step withoutfurther purification.

LCMS (method 5): 468 (M+H)⁺, retention time 0.86 min.

Step 6: Preparation of1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile

A solution of above isomeric mixture of5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamideandN-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide(750 mg, 1.60 mmol) in acetic acid (4.8 mL) was heated to 100° C. for 48hours. After cooling to room temperature, the reaction mixture wasconcentrated in vacuo. The residue was poured into water and extractedwith ethyl acetate (3×100 mL), the combined organic layers washed withbrine, dried over sodium sulfate and concentrated in vacuo. The crudeproduct was purified by chromatography on silica gel (40% ethyl acetatein cyclohexane) to afford the desired product1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile(350 mg) as a solid. LCMS (method E): 450 (M+H)⁺, retention time 1.03min.

¹H NMR (400 MHz, CDCl3) δ ppm 1.37 (t, 3H), 1.59 (m, 2H), 1.93 (m, 2H),3.01 (q, 2H), 4.20 (s, 3H), 4.21 (s, 3H), 7.25 (s, 1H), 7.76 (d, J=2.0Hz, 1H), 8.32 (d, J=2.0 Hz, 1H).

Step 7: Preparation of1-[5-(ethylsulfonimidoyl)-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile(Example P8, Table P)

Sulfoximine formation analogous to Example H1, Step 7.

LCMS (method 5): 481 (M+H)⁺; retention time: 0.85 min.

1H NMR (400 MHz, DMSO-d6) δ ppm 1.14 (t, J=7.40 Hz, 3H) 1.83-1.94 (m,2H) 1.97-2.06 (m, 2H) 3.44-3.66 (m, 2H) 3.86 (s, 3H) 4.12 (s, 3H) 4.56(s, 1H) 7.41 (s, 1H) 8.38 (d, J=2.20 Hz, 1H) 8.90 (d, J=2.20 Hz, 1H).

Example H4: Preparation of1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile(Example P9, Table P)

Step 1: Preparation ofN-[4-amino-6-(trifluoromethylsulfanyl)-3-pyridyl]-4-bromo-2-ethylsulfanyl-N-methyl-benzamide

Under argon, 4-bromo-2-ethylsulfanyl-benzoic acid (prepared as describedin patent WO 2016/120182 (1.96 g, 7.51 mmol)) was suspended indichloromethane (30 mL) and 2 drops of DMF were added. oxalyl dichloride(1.24 g, 0.851 mL, 9.76 mmol) was added dropwise and gas evolution wasobserved. The mixture was stirred 4 hours at room temperature and thenconcentrated in vacuo to give 4-bromo-2-ethylsulfanyl-benzoyl chlorideas product of the first step. Under argon, the crude4-bromo-2-ethylsulfanyl-benzoyl chloride (2.07 g, 7.39 mmol) freshlyprepared, was dissolved in tetrahydrofurane (20 mL) andN3-methyl-6-(trifluoromethylsulfanyl)pyridine-3,4-diamine prepared asdescribed in patent WO 2016/169886 (1.50 g, 6.72 mmol) was added. Theresulting mixture was stirred one night at room temperature then 8 hoursat 70° C. Sodium bicarbonate and water were added after cooling at roomtemperature. The aqueous layer was extracted 2 times with ethyl acetate.The combined organic layer were dried over sodium sulfate, filtered andconcentrated in vacuo to afford a mixture containingN-[4-amino-6-(trifluoromethylsulfanyl)-3-pyridyl]-4-bromo-2-ethylsulfanyl-N-methyl-benzamide.

LCMS (method 1): 450 (M+H)⁺; retention time: 1.14 min.

Step 2: Preparation of2-(4-bromo-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine

N-[4-amino-6-(trifluoromethylsulfanyl)-3-pyridyl]-4-bromo-2-ethylsulfanyl-N-methyl-benzamide(3.4 g, 5.1 mmol) was dissolved in acetic acid (51 mL). The resultingsolution was stirred one night at 120° C. and then cooled down at roomtemperature. Acetic acid was removed under reduced pressure and thecrude was purified by chromatography over silica gel The mixtureobtained was dissolved in ethyl acetate, washed with bicarbonate, driedover sodium sulfate, filtered and concentrated in vacuo to afford2-(4-bromo-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine.

LCMS (method 1): 450 (M+H)⁺; retention time: 1.14 min.

1H NMR (400 MHz, Chloroform) δ ppm 1.29 (t, J=7.34 Hz, 3H) 2.92 (q,J=7.34 Hz, 2H) 3.79 (s, 3H) 7.32 (d, J=8.07 Hz, 1H) 7.50 (dd, J=8.07,1.83 Hz, 1H) 7.61 (d, J=1.83 Hz, 1H) 8.15-8.17 (m, 1H) 8.90 (d, J=1.10Hz, 1H).

Step 3: Preparation of4-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]isoxazole

DMSO (1.11 mL) and water (0.53 mL) were added in a microwave vial underargon and the solution was purged with argon for 5 min. Then2-(4-bromo-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine(0.2 g, 0.446 mmol), 4-isoxazoleboronic acid pinacol ester (0.104 g,0.535 mmol) and potassium fluoride (0.077 g, 1.33 mmol) were added.

Dichloropalladium;triphenylphosphane (0.0031 g, 0.0044 mmol) was added,the resulting mixture was purged with argon for 5 min, stirred for 40min at 90° C. in a micro wave system, cooled down at room temperatureand then poured in ice-water. The aqueous layer was extracted 3 timeswith dichloromethane. Then the milky aqueous layer was filtered and thesolid obtained was dissolved in dichloromethane and added to the organiclayer. The combined organic layers was dried over sodium sulfate,filtered and concentrated in vacuo. The oil obtained was washed withwater. The precipitate formed in water was filtered then dissolved indichloromethane again and the solvent was concentrated in vacuo toafford4-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]isoxazole,which was used as such for the next step.

LCMS (method 1): 437 (M+H)⁺; retention time: 0.95 min.

Step 4: Preparation of2-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]acetonitrile

4-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]isoxazole(236 mg, 0.3785 mmol, 70 mass %) was dissolved in methanol (2 mL) andwater (1.14 mL), and potassium fluoride (1.14 mL, 1.135 mmol) was added.The reaction mixture was stirred for 3 hours at 90° C. The dark redreaction mixture (suspension) was filtered, washed with dichloromethaneand concentrated in vacuo. The crude was purified by chromatography oversilica gel column to afford2-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]acetonitrile.

LCMS (method 1): 409 (M+H)⁺; retention time: 0.98 min.

1H NMR (400 MHz, Chloroform) δ ppm 1.29 (t, J=7.34 Hz, 4H) 2.93 (q,J=7.34 Hz, 2H) 3.80 (s, 3H) 3.89 (s, 2H) 7.34 (dd, J=7.89, 1.65 Hz, 1H)7.47-7.48 (m, 1H) 7.48-7.51 (m, 1H) 8.16-8.18 (m, 1H) 8.92 (d, J=0.73Hz, 1H).

Step 5: Preparation of1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile

1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile(0.108 g, 0.2644 mmol) was dissolved in acetonitrile (1.322 mL). Thendicesium carbonate (0.2584 g, 0.7931 mmol) and 1,2-dibromoethane (0.1490g, 0.0683 mL, 0.7931 mmol) were added. The reaction mixture was stirredunder microwave system at 100° C. for 2 hours. The reaction mixture wasconcentrated in vacuo. The residue was dissolved in ethyl acetate andwashed several times with water and brine. Organic layer was dried oversodium sulfate, filtered and concentrated in vacuo. The crude productwas purified chromatography over silica gel to afford1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile.

LCMS (method 1): 435 (M+H)⁺; retention time: 1.04 min.

¹H NMR (400 MHz, Chloroform) δ ppm 1.28 (t, J=7.34 Hz, 4H) 1.55 (br d,J=2.20 Hz, 2H) 1.86-1.91 (m, 2H) 2.93 (q, J=7.58 Hz, 2H) 3.79 (s, 3H)7.17 (dd, J=7.89, 2.02 Hz, 1H) 7.44-7.47 (m, 1H) 7.52 (d, J=1.83 Hz, 1H)8.16 (d, J=0.73 Hz, 1H) 8.91 (d, J=0.73 Hz, 1H).

Step 6: Synthesis of1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile(Example P9, Table P)

Sulfoximine formation carried out as described in Example H1, step 7.

LCMS (method 1): 466 (M+H)⁺; retention time: 0.86 min.

Example H5: Synthesis of1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile(Example P13, Table P)

Step 1: Preparation of1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile

To a mixture of2-(4-bromo-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridineprepared as described in patent WO 2016/030229 (0.5 g, 1.201 mmol),Pd₂dba₃ (0.056 g, 0.060 mmol) and BINAP (0.077 g, 0.120 mmol) intetrahydrofurane (1.2 mL) were added cyclopropanecarbonitrile (0.090 g,1.32 mmol) and cyclopropylmethylether (1.20 mL) under argon atmosphereat rt. The mixture was cooled down at −25° C. and Lithiumbis(trimethylsilyl)amide (1.3 mL, 1.321 mmol) was added dropwise at −25°C., under argon atmosphere. The mixture was stirred at 80° C. for 2hours. After cooling at room temperature, the mixture was filtered overa pad of celite which was washed with ethyl acetate. The filtrate waswashed with water. The aqueous layer was separated and extracted twicewith ethyl acetate. The organic layers were combined, dried overanhydrous sodium sulfate, filtered, and concentrated in vacuo. The crudeproduct was purified by chromatography over silica gel to afford1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile.

LCMS (method 1): 403 (M+H)⁺; retention time: 1.00 min.

1H NMR (400 MHz, Chloroform) δ ppm 1.27 (t, J=7.34 Hz, 3H) 1.52-1.57 (m,2H) 1.86-1.91 (m, 2H) 2.91 (q, J=7.46 Hz, 2H) 3.82 (s, 3H) 7.18 (dd,J=8.07, 1.83 Hz, 1H) 7.46 (d, J=8.07 Hz, 1H) 7.52 (d, J=1.83 Hz, 1H)8.14 (d, J=0.73 Hz, 1H) 8.95 (s, 1H).

Step 2: Synthesis of1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile(Example P13, Table P)

The desired product was prepared using the standard procedure describedstep 7, example H1.

LCMS (method 1): 434 (M+H)⁺; retention time: 0.83 min.

1H NMR (400 MHz, Chloroform) δ ppm 1.28 (t, J=7.34 Hz, 3H) 1.63-1.68 (m,2H) 1.96-2.01 (m, 2H) 3.42-3.62 (m, 2H) 3.75 (s, 3H) 7.56 (d, J=8.07 Hz,1H) 7.89 (dd, J=7.89, 2.02 Hz, 1H) 8.05 (d, J=1.83 Hz, 1H) 8.10 (d,J=0.73 Hz, 1H) 8.93-8.96 (m, 1H).

Example H5: Synthesis of1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile(Example P15, Table P)

Step 1: Synthesis of methyl 2-ethylsulfanyl-4-isoxazol-4-yl-benzoate

To a solution of methyl 4-bromo-2-ethylsulfanyl-benzoate (WO2016/023954) (250 mg, 0.91 mmol) in dimethyl sulfoxide (8 mL) underargon were added water (4 mL), 4-isoxazoleboronic acid pinacol ester(213 mg, 1.09 mmol) and potassium fluoride (158 mg, 2.73 mmol). Thethick reaction mixture was purged with argon for 5 minutes, thenbis(triphenylphosphine)palladium(II) dichloride (6.4 mg, 0.009 mmol) wasadded. The vial was sealed and the mixture stirred in the microwave at90° C. for 40 minutes. The reaction mixture was poured onto iced-water,and the resulting yellowish suspension filtered and washed with coldwater. This solid was dissolved in dichlormethane, the solution driedover sodium sulfate and reduced to dryness under vacuum to afford methyl2-ethylsulfanyl-4-isoxazol-4-yl-benzoate as a yellowish solid. Thismaterial was used in the next step without further purification.

LCMS (method 1): 262 (M−H)−, retention time 0.88 min.

Step 2: Synthesis of methyl 4-(cyanomethyl)-2-ethylsulfanyl-benzoate

To a solution of methyl 2-ethylsulfanyl-4-isoxazol-4-yl-benzoate (760mg, 2.89 mmol) in methanol (15 mL) was added a 1 M potassium fluoridesolution in water (8.66 mL, 8.66 mmol). The reaction mixture was stirredat reflux for 3 hours. After cooling, the suspension was filtered andthe filtrate concentrated in vacuo. The residue was purified byCombiflash over silicagel to afford methyl4-(cyano-methyl)-2-ethylsulfanyl-benzoate as a gum.

LCMS (method 5): 236 (M+H)⁺, retention time 0.90 min.

¹H NMR (400 MHz, CDCl3) δ ppm 1.42 (t, 3H), 2.99 (q, 2H), 3.80 (s, 2H),3.93 (s, 3H), 7.10 (dd, 1H), 7.28 (d, 1H), 7.99 (d, 1H).

Step 3: Synthesis of methyl4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoate

To a solution of methyl 4-(cyano-methyl)-2-ethylsulfanyl-benzoate (300mg, 1.275 mmol) in acetonitrile (15 mL) were added cesium carbonate(1.24 g, 3.825 mmol) and 1,2-dibromoethane (719 mg, 3.825 mmol). Thereaction mixture was stirred at reflux for 90 minutes. After cooling,the suspension was filtered and the filtrate concentrated in vacuo. Theresidue was purified by Combiflash over silicagel to afford methyl4-(cyano-methyl)-2-ethylsulfanyl-benzoate as an oil.

LCMS (method 1): 262 (M+H)⁺, retention time 0.98 min. ¹H NMR (400 MHz,CDCl3) δ ppm 1.43 (t, 3H), 1.48 (m, 2H), 1.82 (m, 2H), 3.01 (q, 2H),3.92 (s, 3H), 6.88 (dd, 1H), 7.35 (d, 1H), 7.94 (d, 1H).

Step 4: Synthesis of 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid

To a solution of methyl 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoate(198 mg, 0.758 mmol) in a mixture of tetrahydrofurane (9 mL) and water(3 mL) at 0-5° C. was added lithium hydroxide (1.5 eq., 1.137 mmol) andthe reaction mixture was stirred at room temperature overnight. Thesolution was concentrated in vacuo, the residue diluted with t-butylmethyl ether (10 mL) and acidified with a 1 M aqueous hydrochloric acidsolution (10 mL). The organic layer was separated, the aqueous layerextracted with t-butyl methyl ether, the combined organic layers washedwith water and brine, dried over sodium sulfate, filtered andconcentrated in vacuo to afford4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid as a solid. Thismaterial was used in the next step without further purification.

LCMS (method 5): 246 (M−H)−, retention time 0.83 min. ¹H NMR (400 MHz,CDCl3) δ ppm 1.44 (t, 3H), 1.51 (m, 2H), 1.85 (m, 2H), 3.03 (q, 2H),6.90 (dd, 1H), 7.41 (d, 1H), 8.10 (d, 1H).

Step 5 Preparation of1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile

4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid (1.7 g, 6.9 mmol)was dissolved in nitrobenzene (14 mL) andN2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (WO 2017/043342) (1.6g, 1.2 equiv) was added follow by the slow addition of phosphorylchloride (1.6 mL, 17 mmol) at room temperature. The resulting solutionwas heated at 120° C. for 7 hours monitored by TLC and LC-MS. Reactionmass was quenched with 30% sodium hydroxide solution and water (100 mL)was added. The aqueous layer was extracted with ethyl acetate (3×100ml). The combined organic layer was dried over sodium sulfate, filteredand concentrated in vacuo. The crude product was purified bychromatography to afford1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile.

LCMS (method 2): 403 (M+H)⁺; retention time: 1.18 min.

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.26 (t, J=7.34 Hz, 3H) 1.44-1.61(m, 2H) 1.80-1.92 (m, 2H) 2.91 (q, J=7.42 Hz, 2H) 3.78 (s, 3H) 7.16 (dd,J=8.01, 1.77 Hz, 1H) 7.44 (d, J=7.60 Hz, 1H) 7.50 (s, 1H) 8.33 (s, 1H)8.72 (s, 1H).

Step 6: Preparation of1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile(Example P15. Table P)

The desired product was prepared using the standard procedure describedin example H1, step 7.

LCMS (method 1): 434 (M+H)⁺; retention time: 0.88 min.

1H NMR (400 MHz, Chloroform) δ ppm 1.28 (t, J=7.34 Hz, 4H) 1.63-1.68 (m,2H) 1.96-2.01 (m, 2H) 3.41-3.62 (m, 2H) 3.75 (s, 3H) 7.56 (d, J=8.07 Hz,1H) 7.89 (dd, J=7.89, 2.02 Hz, 1H) 8.05 (d, J=1.83 Hz, 1H) 8.10 (d,J=0.73 Hz, 1H) 8.94-8.97 (m, 1H).

Example H6: Synthesis of[5-cyclopropyl-2-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane(Example P16, Table P)

Step 1. Preparation of2-bromo-1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone

A sample of 1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone (preparationdescribed in WO 2016/071214 (1 g, 3.8439 mmol) was suspended inacetonitrile (3 mL) and chloroform (3 mL). Dibromocopper (1.7171 g,7.6879 mmol) was added and the reaction mixture was heated to 70° C. andstirred for 22 hours, after which time LC-MS showed reaction completion.The reaction mixture was filtered through celite and withdichloromethane. The filtrate was concentrated in vacuo and the residueobtained was purified by chromatography over silica gel to afford2-bromo-1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone.

LCMS (method 1): retention time 1.10 min; 339/341 (M+H)⁺.

¹H NMR (400 MHz, DMSO) δ ppm 1.28 (t, J=7.34 Hz, 3H) 3.06 (q, J=7.34 Hz,2H) 4.93 (s, 2H) 8.11 (d, J=1.83 Hz, 1H) 8.58-8.60 (m, 1H).

Step 2: Preparation of2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine

In a three neck flask fitted with reflux condenser,2-bromo-1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone (0.50 g, 1.5 mmol)and 5-(trifluoromethyl)pyridazin-3-amine (CAS [1211591-88-6]) (0.27 g,1.5 mmol) were suspended in acetonitrile (11 mL) and magnesium oxide(0.12 g, 2.9 mmol) was added. The resulting mixture was heated to 90° C.and stirred overnight. The reaction mixture was filtered and thefiltrate was concentrated in vacuo. The resulting solid was dissolved inethyl acetate and washed once with NaHCO3 sat. sol. The organic layerwas pre-dried with brine, dried over sodium sulphate, filtered andconcentrated in vacuo. The crude product was purified by chromatographyover silica gel to afford2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine.

LCMS (method 1): retention time 1.15 min; 403/405 (M+H)⁺.

1H NMR (400 MHz, Chloroform) δ ppm 1.44 (t, J=7.34 Hz, 3H) 3.04 (q,J=7.34 Hz, 2H) 7.82 (d, J=1.83 Hz, 1H) 8.33-8.39 (m, 1H) 8.57 (dd,J=3.85, 2.02 Hz, 2H) 8.81-8.86 (m, 1H).

Step 3: Preparation of2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine

In a 100 ml-3-necked flask toluene (14 mL) and water (0.69 mL) wasplaced and flushed with argon 5 min. Under argon,2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine(0.30 g, 0.74 mmol), cyclopropylboronic acid (0.087 g, 0.97 mmol),tripotassium phosphate (0.58 g, 2.6 mmol), tricyclohexylphosphane (0.022g, 0.074 mmol) and Palladium (II) acetate (0.0084 g, 0.050 eq, 0.037mmol) were added. The brown reaction mixture was heated up to 110° C.and stirred one night. Then the mixture was cooled down at roomtemperature and water and ethyl acetate were added. The resultingmixture was filtered over celite and celite cake was washed by ethylacetate. The organic layer was separated, dried over sodium sulfate,filtered and concentrated under vacuum. The crude was purified bychromatography over silica gel to afford2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine.

LCMS (method 1): retention time 1.08 min; 365 (M+H)⁺.

1H NMR (400 MHz, Chloroform) δ ppm 0.81-0.86 (m, 2H) 1.09-1.16 (m, 2H)1.39 (t, J=7.34 Hz, 3H) 1.94-2.03 (m, 1H) 3.00 (q, J=7.34 Hz, 2H)7.36-7.39 (m, 1H) 8.33 (d, J=1.83 Hz, 1H) 8.33 (s, 1H) 8.54 (d, J=2.20Hz, 1H) 8.83-8.86 (m, 1H).

Step 4: Preparation of[5-cyclopropyl-2-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane((Example P16, Table P).)

2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine(0.07 g, 0.1921 mmol) was suspended in methanol (0.5763 mL) andPhI(OAc)₂ (0.1894 g, 0.5763 mmol) and ammonium carbamate (0.03826 g,0.4802 mmol) were added at room temperature. The reaction was stirred atroom temperature and after 45 min, was quenched with iced water andsodium thiosulfate. The aqueous layer was extracted twice with acetated'ethyl. The organic layers were combined washed with brine, dried overanhydrous sodium sulfate, filtered and concentrated under. The crudeproduct was purified by chromatography over silica gel to afford[5-cyclopropyl-2-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]-ethyl-imino-oxo-X⁶-sulfane.

LCMS (method 1): retention time 0.87 min; 396 (M+H)⁺.

1H NMR (400 MHz, Chloroform) δ ppm 0.89-0.95 (m, 2H) 1.18-1.25 (m, 2H)1.36 (t, J=7.52 Hz, 3H) 2.08 (tt, J=8.44, 5.14 Hz, 1H) 3.21-3.37 (br s,1H) 3.71-3.98 (m, 2H) 8.19 (d, J=2.20 Hz, 1H) 8.26-8.29 (m, 1H) 8.58 (d,J=2.20 Hz, 1H) 8.64 (d, J=2.20 Hz, 1H) 8.71-8.74 (m, 1H).

Example H7: Synthesis of[5-cyclopropyl-2-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane(Example P7, Table P)

Step 1: Preparation of 2,5-dibromo-3-ethylsulfanyl-pyridine

A solution of diethyldisulfide (7.76 g, 63.5 mmol, 2.00 equiv.) andtert-butyl nitrite (4.91 g, 47.6 mmol, 1.50 equiv.) in DCE (60 mL) andDCM (40 mL) was heated to 40° C. To this mixture was slowly added asolution of 2,5-dibromopyridin-3-amine (8.00 g, 31.7 mmol, 1.00 equiv.)in dichloroethane (200 mL) slowly over 90 min and the reaction mixturewas stirred for additional 1 h at 40° C. After completion of thereaction, the reaction mass was cooled, diluted with water (100 mL), andextracted with dichloromethane (2×100 mL). The organic layer wasseparated, combined organic layers were dried over sodium sulfate,filtered and concentrated in vacuo. The crude product was purified bycolumn chromatography (silica gel, 5-15% ethyl acetate/cyclohexane) toafford 2,5-dibromo-3-ethylsulfanyl-pyridine.

LCMS (method 4): 296 (M+H)⁺, retention time 1.16 min.

¹H NMR (400 MHz, CDCl₃) δ/ppm: 1.32 (t, 3H), 2.98 (m, 2H), 7.52 (s, 1H)8.19 (s, 1H).

Step 2: Preparation of (5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazine

To a solution of 2,5-dibromo-3-ethylsulfanyl-pyridine (1 g, 3.3669 mmol)in 1,4-dioxane (10.34 g) hydrazine monohydrate (1.0113 g, 20.201 mmol)was added and the resulting mixture was stirred at 120° C. for 10 hours.After completion of reaction, the mixture was diluted with water (30 ml)and extracted with ethyl acetate. The combined organic layers werewashed with water (20 ml), dried with sodium sulfate, filtered andconcentrated in vacuo to afford(5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazine.

LCMS: 250 (M+H)⁺, retention time 0.6 min.

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.26 (t, 3H) 2.81 (q, 2H) 3.10 (br2H) 6.67 (br s, 1H) 7.65 (d, 1H) 8.15 (d, 1H).

Step 3: Preparation of4-[2-(5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazino]-6-(trifluoromethyl)pyridine-3-carboxylic acid

4-chloro-6-(trifluoromethyl)pyridine-3-carboxylic acid (CAS[1060810-66-3]) (20 g, 88.672 mmol),(5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazine (33.005 g, 133.01 mmol) andpentan-1-ol (120 mL) were mixed and the mixture was stirred at 110° C.for 15 hours. After completion of reaction, the mixture was concentratedin vacuo to remove all of the pentanol. The residue obtained wasco-evaporated with toluene. The crude product was diluted with water(100 ml), brine (100 ml) and extracted with ethyl acetate (3×200 ml).The combined organic layer was dried over sodium sulfate, filtered andconcentrated in vacuo. The solid obtained was triturated withcyclohexane to afford4-[2-(5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazino]-6-(trifluoromethyl)pyridine-3-carboxylicacid.

LCMS (method 5): retention time 1.50 min, 439 (M+2)⁺.

1H NMR (400 MHz, DMSO-d6) δ ppm 1.26 (t, 3H) 3.05 (q, 2H) 7.16 (s, 1H)7.89 (d, 1H) 8.11 (d, 1H) 8.77 (s, 1H) 8.88 (s, 1H) 9.83 (s, 1H)13.38-14.36 (m, 1H).

Step 4: Preparation of2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-3-chloro-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine

4-[2-(5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazino]-6-(trifluoromethyl)pyridine-3-carboxylicacid (22.87 mmol, 10 g) was solved in phosphorus oxychloride (100 mL)and the resulting mixture was heated at 110° C. The clear solutionobtained at 110° C. was refluxed for 50 min. After completion ofreaction, the mixture was concentrated (phosphorus oxychloride distilledoff under reduced pressure) and the reaction was diluted withdichloromethane (110 ml) poured into ice water (200 mL). The aqueouslayer was extracted with dichlormethane (2×100 ml). The combined organiclayer was washed with water (200 ml), dried over sodium sulfate,filtered and concentrated in vacuo. The crude product was purified bychromatography over silica gel to afford2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-3-chloro-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine.

LCMS: 437 (M+H)⁺, retention time 1.21 min.

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.34 (m, 3H) 2.85 (m, 2H) 7.92 (S,2H) 8.02 (m, 1H) 8.60 (m, 1H) 9.32 (m, 1H).

Step 5: Preparation of2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine

2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-3-chloro-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine(0.2 mmol, 0.1 g) was solved in acetic acid (2 mL) and zinc (0.5 mmol,0.03 g) was added slowly to the mixture. The reaction mass was stirredat 55° C. for 40 min. The reaction was monitored by LCMS & TLC. Aftercompletion, the reaction mixture was poured into water (30 ml), and theresultant solution was extracted with ethyl acetate (20 ml×3). Thecombined organic layer was washed with aqueous saturated sodium chloridesolution (30 ml), dried over anhydrous sodium sulfate, filtered andconcentrated in vacuo. The residue was subjected to silica gel columnchromatography to afford2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine.

H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.29 (m, 4H) 2.95 (m, 2H) 7.85 (m,1H) 8.35 (m, 1H) 8.38 (d, 1H) 8.95 (m, 1H) 9.44 (m, 1H).

LCMS: retention time 1.6 min, 403 (M+H)⁺.

Step 6: Preparation of2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine

In a microwave vial were added2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine(0.1 g, 0.2 mmol), cyclopropylboronic acid (0.03 g., 0.3 mmol),tripotassium phosphate (0.2 g, 0.9 mmol), tricyclohexylphosphane (0.007g, 0.02 mmol) in toluene (2 mL) and water (1 mL). The reaction mass waspurged with nitrogen for 30 min. To this was then added palladium(II)acetate (0.003 g., 0.01 mmol) and the reaction mixture was stirred at150° C. under microwave for 4 hours. Then at room temperature, reactionmixture was diluted with ethyl acetate (20 mL) and washed with water (20mL). The organic layer was washed with water (20 ml), dried organiclayer over sodium sulfate, filtered and concentrated in vacuo. Thecompound was isolated by chromatography over silica gel to afford2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine.

LCMS: 365 (M+H)⁺, retention time 1.12 min.

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.86 (m, 2H) 1.13 (br, 2H) 1.23 (m,4H) 2.90 (q, 2H) 7.47 (d, 1H) 8.13 (m, 2H) 8.94 (s, 1H) 9.40 (m, 1H).

Step 7: Synthesis of[5-cyclopropyl-2-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfaneExample P7, Table P)

The desired product was prepared in using the standard method describedin example H1, Step 7.

LCMS (method 5): retention time 0.94 min, 396 (M+H)⁺.

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.25 (m, 4H) 1.44 (m, 3H) 2.16 (m,1H) 3.87 (m, 2H) 8.06 (s, 1H) 8.29 (d, 1H) 8.56 (d, 1H) 8.87 (d, 1H)9.40 (s, 1H).

Example H8: Synthesis of[5-cyclopropyl-2-[5-(trifluoromethylsulfanyl)-1,3-benzoxazol-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane(Example P18, Table P)

The desired product was prepared by using the standard method describedin Example H1, Step 7 starting from2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(trifluoromethylsulfanyl)-1,3-benzoxazole(known from WO19/009307).

LCMS (method 5): 428 (M+H)⁺, retention time: 1.03 min.

Further compounds of the invention can be prepared analogously to themethod described above. Compounds prepared to further illustrate theinvention are listed in Table P.

[M + H] RT Entry IUPAC name STRUCTURE (min) (measured) Method MP °C P11-[5-(ethylsulfonimidoyl)-6-[7- methyl-3- (trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl] cyclopropanecarboxamide

0.87 454 5 253-255 P2 1-[3-(ethylsulfonimidoyl)-4-[3- methyl-6-(trifluoromethyl)imidazo[4,5- b]pyridin-2-yl]phenyl]cyclopropanecarboxamide

0.88 452 5 235-237 P3 [5-cyclopropyl-2-[3-methyl-6-(trifluoromethylsulfonyl) imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶- sulfane

0.91 474 1 — P4 [5-cyclopropyl-2-[3-methyl-6- (trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]-3- pyridyl]-ethyl-imino-oxo-λ⁶- sulfane

0.90 442 1 — P5 [5-cyclopropyl-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5- c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane

0.85 411 1 — P6 1-[5-(ethylsulfonimidoyl)-6-[3- methyl-6-(trifluoromethyl)imidazo[4,5- b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile

0.87 435 1 — P7 [5-cyclopropyl-2-[6- (trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]- ethyl-imino-oxo-λ⁶-sulfane

0.94 396 5 75-77 P8 1-[5-(ethylsulfonimidoyl)-6-[5-methoxy-3-methyl-4-oxo-6- (trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl] cyclopropanecarbonitrile

0.85 481 5 163-165 P9 1-[3-(ethylsulfonimidoyl)-4-[3- methyl-6-(trifluoromethylsulfanyl) imidazo[4,5-c]pyridin-2- yl]phenyl]cyclopropanecarbonitrile

0.86 466 1 191-193 P10 1-[5-(ethylsulfonimidoyl)-6-[7- methyl-3-(trifluoromethyl)imidazo[4,5- c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile

0.82 436 5 182-184 P11 [5-cyclopropyl-2-[7-methyl-3-(trifluoromethyl)imidazo[4,5- c]pyridazin-6-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane

0.84 411 1 — P12 [5-cyclopropyl-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5- b]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane

0.89 410 1 — P13 1-[3-(ethylsulfonimidoyl)-4-[3- methyl-6-(trifluoromethyl)imidazo[4,5- c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile

0.83 434 1 — P14 1-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5- c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl] cyclopropanecarbonitrile

0.92 479 5 176-178 P15 1-[3-(ethylsulfonimidoyl)-4-[3- methyl-6-(trifluoromethyl)imidazo[4,5- b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile

0.88 434 1 117-117 P16 [5-cyclopropyl-2-[7-(trifluoromethyl)imidazo[1,2- b]pyridazin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane

0.87 396 1 119-121 P17 1-[5-(ethylsulfonimidoyl)-6-[6-(trifluoromethyl)pyrazolo[4,3- c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile

0.91 421 5 170-172 P18 [5-cyclopropyl-2-[5- (trifluoromethylsulfanyl)-l,3- benzoxazol-2-yl]-3-pyridyl]- ethyl-imino-oxo-λ⁶-sulfane

1.03 428 5 224-226 P19 [5-cyclopropyl-2-[5- (trifluoromethylsulfonyl)-l,3- benzoxazol-2-yl]-3-pyridyl]- ethyl-imino-oxo-λ⁶-sulfane

1.10 460 5 —

The activity of the compositions according to the invention can bebroadened considerably, and adapted to prevailing circumstances, byadding other insecticidally, acaricidally and/or fungicidally activeingredients. The mixtures of the compounds of formula I with otherinsecticidally, acaricidally and/or fungicidally active ingredients mayalso have further surprising advantages which can also be described, ina wider sense, as synergistic activity. For example, better tolerance byplants, reduced phytotoxicity, insects can be controlled in theirdifferent development stages or better behaviour during theirproduction, for example during grinding or mixing, during their storageor during their use. Suitable additions to active ingredients here are,for example, representatives of the following classes of activeingredients: organophosphorus compounds, nitrophenol derivatives,thioureas, juvenile hormones, formamidines, benzophenone derivatives,ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinatedhydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides,neonicotinoids and Bacillus thuringiensis preparations.

The following mixtures of the compounds of formula I with activeingredients are preferred (the abbreviation “TX” means “one compoundselected from the group consisting of the compounds described in TablesY-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 and Table P of thepresent invention”):

an adjuvant selected from the group of substances consisting ofpetroleum oils (alternative name) (628)+TX,

an acaricide selected from the group of substances consisting of1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910)+TX,2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name)(1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name)(1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981)+TX,abamectin (1)+TX, acequinocyl (3)+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, alpha-cypermethrin(202)+TX, amidithion (870)+TX, amidoflumet [CCN]+TX, amidothioate(872)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz(24)+TX, aramite (881)+TX, arsenous oxide (882)+TX, AVI 382 (compoundcode)+TX, AZ 60541 (compound code)+TX, azinphos-ethyl (44)+TX,azinphos-methyl (45)+TX, azobenzene (IUPAC name) (888)+TX, azocyclotin(46)+TX, azothoate (889)+TX, benomyl (62)+TX, benoxafos (alternativename) [CCN]+TX, benzoximate (71)+TX, benzyl benzoate (IUPAC name)[CCN]+TX, bifenazate (74)+TX, bifenthrin (76)+TX, binapacryl (907)+TX,brofenvalerate (alternative name)+TX, bromocyclen (918)+TX, bromophos(920)+TX, bromophos-ethyl (921)+TX, bromopropylate (94)+TX, buprofezin(99)+TX, butocarboxim (103)+TX, butoxycarboxim (104)+TX, butylpyridaben(alternative name)+TX, calcium polysulfide (IUPAC name) (111)+TX,camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX,carbofuran (118)+TX, carbophenothion (947)+TX, CGA 50′439 (developmentcode) (125)+TX, chinomethionat (126)+TX, chlorbenside (959)+TX,chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorfenapyr (130)+TX, chlorfenethol (968)+TX, chlorfenson (970)+TX,chlorfensulfide (971)+TX, chlorfenvinphos (131)+TX, chlorobenzilate(975)+TX, chloromebuform (977)+TX, chloromethiuron (978)+TX,chloropropylate (983)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl(146)+TX, chlorthiophos (994)+TX, cinerin 1 (696)+TX, cinerin II(696)+TX, cinerins (696)+TX, clofentezine (158)+TX, closantel(alternative name) [CCN]+TX, coumaphos (174)+TX, crotamiton (alternativename) [CCN]+TX, crotoxyphos (1010)+TX, cufraneb (1013)+TX, cyanthoate(1020)+TX, cyflumetofen (CAS Reg. No.: 400882-07-7)+TX, cyhalothrin(196)+TX, cyhexatin (199)+TX, cypermethrin (201)+TX, DCPM (1032)+TX, DDT(219)+TX, demephion (1037)+TX, demephion-O (1037)+TX,demephion-S(1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX,demeton-O (1038)+TX, demeton-O-methyl (224)+TX, demeton-S(1038)+TX,demeton-S-methyl (224)+TX, demeton-S-methylsulfon (1039)+TX,diafenthiuron (226)+TX, dimpropyridaz+TX, dialifos (1042)+TX, diazinon(227)+TX, dichlofluanid (230)+TX, dichlorvos (236)+TX, dicliphos(alternative name)+TX, dicofol (242)+TX, dicrotophos (243)+TX,dienochlor (1071)+TX, dimefox (1081)+TX, dimethoate (262)+TX, dinactin(alternative name) (653)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX,dinobuton (269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX, dinocap-6[CCN]+TX, dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon(1097)+TX, dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl sulfone(IUPAC name) (1103)+TX, disulfiram (alternative name) [CCN]+TX,disulfoton (278)+TX, DNOC (282)+TX, dofenapyn (1113)+TX, doramectin(alternative name) [CCN]+TX, endosulfan (294)+TX, endothion (1121)+TX,EPN (297)+TX, eprinomectin (alternative name) [CCN]+TX, ethion (309)+TX,ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos (1142)+TX,fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide (330)+TX,fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad (alternativename)+TX, fenpyroximate (345)+TX, fenson (1157)+TX, fentrifanil(1161)+TX, fenvalerate (349)+TX, fipronil (354)+TX, fluacry-pyrim(360)+TX, fluazuron (1166)+TX, flubenzimine (1167)+TX, flucycloxuron(366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenoxuron(370)+TX, flumethrin (372)+TX, fluorbenside (1174)+TX, fluvalinate(1184)+TX, FMC 1137 (development code) (1185)+TX, formetanate (405)+TX,formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate(1193)+TX, gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX,heptenophos (432)+TX, hexadecyl cyclopropanecarboxylate (IUPAC/ChemicalAbstracts name) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPACname) (542)+TX, isocarbophos (alternative name) (473)+TX, isopropylO-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX,ivermectin (alternative name) [CCN]+TX, jasmolin 1 (696)+TX, jasmolin II(696)+TX, jodfenphos (1248)+TX, lindane (430)+TX, lufenuron (490)+TX,malathion (492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan(1261)+TX, mesulfen (alternative name) [CCN]+TX, methacrifos (1266)+TX,methamidophos (527)+TX, methidathion (529)+TX, methiocarb (530)+TX,methomyl (531)+TX, methyl bromide (537)+TX, metolcarb (550)+TX,mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX,milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512(compound code)+TX, nifluridide (1309)+TX, nikkomycins (alternativename) [CCN]+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloridecomplex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compoundcode)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydeprofos (1324)+TX,oxydisulfoton (1325)+TX, pp′-DDT (219)+TX, parathion (615)+TX,permethrin (626)+TX, petroleum oils (alternative name) (628)+TX,phenkapton (1330)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon (639)+TX,phoxim (642)+TX, pirimiphos-methyl (652)+TX, polychloroterpenes(traditional name) (1347)+TX, polynactins (alternative name) (653)+TX,proclonol (1350)+TX, profenofos (662)+TX, promacyl (1354)+TX, propargite(671)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion(1360)+TX, prothoate (1362)+TX, pyrethrin I (696)+TX, pyrethrin II(696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos(711)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX,RA-17 (development code) (1383)+TX, rotenone (722)+TX, schradan(1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name)[CCN]+TX, SI-0009 (compound code)+TX, sophamide (1402)+TX, spirodiclofen(738)+TX, spiromesifen (739)+TX, SSI-121 (development code) (1404)+TX,sulfiram (alternative name) [CCN]+TX, sulfluramid (750)+TX, sulfotep(753)+TX, sulfur (754)+TX, SZI-121 (development code) (757)+TX,tau-fluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP (1417)+TX, terbam(alternative name)+TX, tetrachlorvinphos (777)+TX, tetradifon (786)+TX,tetranactin (alternative name) (653)+TX, tetrasul (1425)+TX, thiafenox(alternative name)+TX, thiocarboxime (1431)+TX, thiofanox (800)+TX,thiometon (801)+TX, thioquinox (1436)+TX, thuringiensin (alternativename) [CCN]+TX, triamiphos (1441)+TX, triarathene (1443)+TX, triazophos(820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX,trifenofos (1455)+TX, trinactin (alternative name) (653)+TX, vamidothion(847)+TX, vaniliprole [CCN] and YI-5302 (compound code)+TX, an algicideselected from the group of substances consisting of bethoxazin [CCN]+TX,copper dioctanoate (IUPAC name) (170)+TX, copper sulfate (172)+TX,cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen (232)+TX, endothal(295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX, nabam (566)+TX,quinoclamine (714)+TX, quinonamid (1379)+TX, simazine (730)+TX,triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide(IUPAC name) (347)+TX,

an anthelmintic selected from the group of substances consisting ofabamectin (1)+TX, crufomate (1011)+TX, doramectin (alternative name)[CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin(alternative name) [CCN]+TX, ivermectin (alternative name) [CCN]+TX,milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternativename) [CCN]+TX, piperazine [CCN]+TX, selamectin (alternative name)[CCN]+TX, spinosad (737) and thiophanate (1435)+TX,

an avicide selected from the group of substances consisting ofchloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX,pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX, a bactericideselected from the group of substances consisting of1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copperdioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name)(169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione(1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde(404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin(483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickelbis(dimethyldithiocarbamate) (IUPAC name) (1308)+TX, nitrapyrin(580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, oxytetracycline(611)+TX, potassium hydroxyquinoline sulfate (446)+TX, probenazole(658)+TX, streptomycin (744)+TX, streptomycin sesquisulfate (744)+TX,tecloftalam (766)+TX, and thiomersal (alternative name) [CCN]+TX,

a biological agent selected from the group of substances consisting ofAdoxophyes orana GV (alternative name) (12)+TX, Agrobacteriumradiobacter (alternative name) (13)+TX, Amblyseius spp. (alternativename) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX,Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis(alternative name) (33)+TX, Aphidius colemani (alternative name)(34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographacalifornica NPV (alternative name) (38)+TX, Bacillus firmus (alternativename) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX,Bacillus thuringiensis Berliner (scientific name) (51)+TX, Bacillusthuringiensis subsp. aizawai (scientific name) (51)+TX, Bacillusthuringiensis subsp. israelensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. japonensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. kurstaki (scientific name) (51)+TX, Bacillusthuringiensis subsp. tenebrionis (scientific name) (51)+TX, Beauveriabassiana (alternative name) (53)+TX, Beauveria brongniartii (alternativename) (54)+TX, Chrysoperla carnea (alternative name) (151)+TX,Cryptolaemus montrouzieri (alternative name) (178)+TX, Cydia pomonellaGV (alternative name) (191)+TX, Dacnusa sibirica (alternative name)(212)+TX, Diglyphus isaea (alternative name) (254)+TX, Encarsia formosa(scientific name) (293)+TX, Eretmocerus eremicus (alternative name)(300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX,Heterorhabditis bacteriophora and H. megidis (alternative name)(433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastixdactylopii (alternative name) (488)+TX, Macrolophus caliginosus(alternative name) (491)+TX, Mamestra brassicae NPV (alternative name)(494)+TX, Metaphycus helvolus (alternative name) (522)+TX, Metarhiziumanisopliae var. acridum (scientific name) (523)+TX, Metarhiziumanisopliae var. anisopliae (scientific name) (523)+TX, Neodiprionsertifer NPV and N. lecontei NPV (alternative name) (575)+TX, Orius spp.(alternative name) (596)+TX, Paecilomyces fumosoroseus (alternativename) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX,Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientificname) (741)+TX, Steinernema bibionis (alternative name) (742)+TX,Steinernema carpocapsae (alternative name) (742)+TX, Steinernema feltiae(alternative name) (742)+TX, Steinernema glaseri (alternative name)(742)+TX, Steinernema riobrave (alternative name) (742)+TX, Steinernemariobravis (alternative name) (742)+TX, Steinernema scapterisci(alternative name) (742)+TX, Steinernema spp. (alternative name)(742)+TX, Trichogramma spp. (alternative name) (826)+TX, Typhlodromusoccidentalis (alternative name) (844) and Verticillium lecanii(alternative name) (848)+TX,

a soil sterilant selected from the group of substances consisting ofiodomethane (IUPAC name) (542) and methyl bromide (537)+TX,

a chemosterilant selected from the group of substances consisting ofapholate [CCN]+TX, bisazir (alternative name) [CCN]+TX, busulfan(alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif(alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa[CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid[CCN]+TX, penfluron (alternative name) [CCN]+TX, tepa [CCN]+TX,thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name)[CCN]+TX, tretamine (alternative name) [CCN] and uredepa (alternativename) [CCN]+TX,

an insect pheromone selected from the group of substances consisting of(E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX,(E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX,(E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX,(E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX,(Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal(IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name)(437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX,(Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al(IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX,(Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX,(7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX,(9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX,(9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX,14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin(alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX,codlelure (alternative name) [CCN]+TX, codlemone (alternative name)(167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX,dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate(IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name)(284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name)[CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternativename) (420)+TX, grandlure (421)+TX, grandlure I (alternative name)(421)+TX, grandlure II (alternative name) (421)+TX, grandlure III(alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX,hexalure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol(alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX,lineatin (alternative name) [CCN]+TX, litlure (alternative name)[CCN]+TX, looplure (alternative name) [CCN]+TX, medlure [CCN]+TX,megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternativename) (540)+TX, muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate(IUPAC name) (588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name)(589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternativename) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX,sordidin (alternative name) (736)+TX, sulcatol (alternative name)[CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure(839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B₁(alternative name) (839)+TX, trimedlure B₂ (alternative name) (839)+TX,trimedlure C (alternative name) (839) and trunc-call (alternative name)[CCN]+TX,

an insect repellent selected from the group of substances consisting of2-(octylthio)ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX,butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name)(1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name)(1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX,dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide[CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX,oxamate [CCN] and picaridin [CCN]+TX, an insecticide selected from thegroup of substances consisting of 1-dichloro-1-nitroethane(IUPAC/Chemical Abstracts name) (1058)+TX,1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), +TX,1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX,1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX,1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX,2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name)(1451)+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate(IUPAC name) (1066)+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate(IUPAC/Chemical Abstracts name) (1109)+TX, 2-(2-butoxyethoxy)ethylthiocyanate (IUPAC/Chemical Abstracts name) (935)+TX,2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ChemicalAbstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name)(986)+TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX,2-imidazolidone (IUPAC name) (1225)+TX, 2-isovalerylindan-1,3-dione(IUPAC name) (1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate(IUPAC name) (1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name)(1433)+TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX,3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX,4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name)(1285)+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPACname) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX,acethion (alternative name) [CCN]+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, acrylonitrile (IUPAC name) (861)+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX, allethrin (17)+TX,allosamidin (alternative name) [CCN]+TX, allyxycarb (866)+TX,alpha-cypermethrin (202)+TX, alpha-ecdysone (alternative name) [CCN]+TX,aluminium phosphide (640)+TX, amidithion (870)+TX, amidothioate(872)+TX, aminocarb (873)+TX, amiton (875)+TX, amiton hydrogen oxalate(875)+TX, amitraz (24)+TX, anabasine (877)+TX, athidathion (883)+TX, AVI382 (compound code)+TX, AZ 60541 (compound code)+TX, azadirachtin(alternative name) (41)+TX, azamethiphos (42)+TX, azinphos-ethyl(44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX, Bacillusthuringiensis delta endotoxins (alternative name) (52)+TX, bariumhexafluorosilicate (alternative name) [CCN]+TX, barium polysulfide(IUPAC/Chemical Abstracts name) (892)+TX, barthrin [CCN]+TX, Bayer22/190 (development code) (893)+TX, Bayer 22408 (development code)(894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX, bensultap (66)+TX,beta-cyfluthrin (194)+TX, beta-cypermethrin (203)+TX, bifenthrin(76)+TX, bioallethrin (78)+TX, bioallethrin S-cyclopentenyl isomer(alternative name) (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin(908)+TX, bioresmethrin (80)+TX, bis(2-chloroethyl) ether (IUPAC name)(909)+TX, bistrifluron (83)+TX, borax (86)+TX, brofenvalerate(alternative name)+TX, bromfenvinfos (914)+TX, bromocyclen (918)+TX,bromo-DDT (alternative name) [CCN]+TX, bromophos (920)+TX,bromophos-ethyl (921)+TX, bufencarb (924)+TX, buprofezin (99)+TX,butacarb (926)+TX, butathiofos (927)+TX, butocarboxim (103)+TX, butonate(932)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX,calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX,carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbondisulfide (IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride(IUPAC name) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX,cartap (123)+TX, cartap hydrochloride (123)+TX, cevadine (alternativename) (725)+TX, chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone(963)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos(131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform[CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos(990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX,chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin I (696)+TX,cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin (alternativename)+TX, cismethrin (80)+TX, clocythrin (alternative name)+TX,cloethocarb (999)+TX, closantel (alternative name) [CCN]+TX,clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate[CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate(1006)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos(1010)+TX, crufomate (1011)+TX, cryolite (alternative name) (177)+TX, CS708 (development code) (1012)+TX, cyanofenphos (1019)+TX, cyanophos(184)+TX, cyanthoate (1020)+TX, cyclethrin [CCN]+TX, cycloprothrin(188)+TX, cyfluthrin (193)+TX, cyhalothrin (196)+TX, cypermethrin(201)+TX, cyphenothrin (206)+TX, cyromazine (209)+TX, cythioate(alternative name) [CCN]+TX, d-limonene (alternative name) [CCN]+TX,d-tetramethrin (alternative name) (788)+TX, DAEP (1031)+TX, dazomet(216)+TX, DDT (219)+TX, decarbofuran (1034)+TX, deltamethrin (223)+TX,demephion (1037)+TX, demephion-O (1037)+TX, demephion-S(1037)+TX,demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX,demeton-O-methyl (224)+TX, demeton-S(1038)+TX, demeton-S-methyl(224)+TX, demeton-S-methylsulphon (1039)+TX, diafenthiuron (226)+TX,dialifos (1042)+TX, diamidafos (1044)+TX, diazinon (227)+TX, dicapthon(1050)+TX, dichlofenthion (1051)+TX, dichlorvos (236)+TX, dicliphos(alternative name)+TX, dicresyl (alternative name) [CCN]+TX, dicrotophos(243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron(250)+TX, dilor (alternative name) [CCN]+TX, dimefluthrin [CCN]+TX,dimefox (1081)+TX, dimetan (1085)+TX, dimethoate (262)+TX, dimethrin(1083)+TX, dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex(1089)+TX, dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam(1094)+TX, dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan(1099)+TX, dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion(1102)+TX, disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX,doramectin (alternative name) [CCN]+TX, DSP (1115)+TX, ecdysterone(alternative name) [CCN]+TX, EI 1642 (development code) (1118)+TX,emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC (1120)+TX,empenthrin (292)+TX, endosulfan (294)+TX, endothion (1121)+TX, endrin(1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane (1124)+TX,eprinomectin (alternative name) [CCN]+TX, esfenvalerate (302)+TX,etaphos (alternative name) [CCN]+TX, ethiofencarb (308)+TX, ethion(309)+TX, ethiprole (310)+TX, ethoate-methyl (1134)+TX, ethoprophos(312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alternativename) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride(chemical name) (1136)+TX, ethylene oxide [CCN]+TX, etofenprox (319)+TX,etrimfos (1142)+TX, EXD (1143)+TX, famphur (323)+TX, fenamiphos(326)+TX, fenazaflor (1147)+TX, fenchlorphos (1148)+TX, fenethacarb(1149)+TX, fenfluthrin (1150)+TX, fenitrothion (335)+TX, fenobucarb(336)+TX, fenoxacrim (1153)+TX, fenoxycarb (340)+TX, fenpirithrin(1155)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX,fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX,fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX,flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX,flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX,flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX,flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code)(1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanatehydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX,fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX,fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX,gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX,guazatine acetates (422)+TX, GY-81 (development code) (423)+TX,halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD(1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, heterophos[CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX,hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX,imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX,iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX,isobenzan (1232)+TX, isocarbophos (alternative name) (473)+TX, isodrin(1235)+TX, isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX,isopropyl O-(methoxy-aminothiophosphoryl)salicylate (IUPAC name)(473)+TX, isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion(480)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX,jasmolin II (696)+TX, jodfenphos (1248)+TX, juvenile hormone I(alternative name) [CCN]+TX, juvenile hormone II (alternative name)[CCN]+TX, juvenile hormone III (alternative name) [CCN]+TX, kelevan(1249)+TX, kinoprene (484)+TX, lambda-cyhalothrin (198)+TX, leadarsenate [CCN]+TX, lepimectin (CCN)+TX, leptophos (1250)+TX, lindane(430)+TX, lirimfos (1251)+TX, lufenuron (490)+TX, lythidathion(1253)+TX, m-cumenyl methylcarbamate (IUPAC name) (1014)+TX, magnesiumphosphide (IUPAC name) (640)+TX, malathion (492)+TX, malonoben(1254)+TX, mazidox (1255)+TX, mecarbam (502)+TX, mecarphon (1258)+TX,menazon (1260)+TX, mephosfolan (1261)+TX, mercurous chloride (513)+TX,mesulfenfos (1263)+TX, metaflumizone (CCN)+TX, metam (519)+TX,metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX,methacrifos (1266)+TX, methamidophos (527)+TX, methanesulfonyl fluoride(IUPAC/Chemical Abstracts name) (1268)+TX, methidathion (529)+TX,methiocarb (530)+TX, methocrotophos (1273)+TX, methomyl (531)+TX,methoprene (532)+TX, methoquin-butyl (1276)+TX, methothrin (alternativename) (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX, methylbromide (537)+TX, methyl isothiocyanate (543)+TX, methylchloroform(alternative name) [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin[CCN]+TX, metolcarb (550)+TX, metoxadiazone (1288)+TX, mevinphos(556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime(alternative name) [CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naftalofos (alternative name) [CCN]+TX, naled (567)+TX,naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170(development code) (1306)+TX, NC-184 (compound code)+TX, nicotine(578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram(579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250(compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron(585)+TX, noviflumuron (586)+TX, 0-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate (IUPAC name) (1057)+TX, 0,0-diethyl0-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name)(1074)+TX, 0,0-diethyl 0-6-methyl-2-propylpyrimidin-4-ylphosphorothioate (IUPAC name) (1075)+TX, O,O,O′,O′-tetrapropyldithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name)(593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl(609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT(219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX,parathion-methyl (616)+TX, penfluron (alternative name) [CCN]+TX,pentachlorophenol (623)+TX, pentachlorophenyl laurate (IUPAC name)(623)+TX, permethrin (626)+TX, petroleum oils (alternative name)(628)+TX, PH 60-38 (development code) (1328)+TX, phenkapton (1330)+TX,phenothrin (630)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosnichlor (1339)+TX,phosphamidon (639)+TX, phosphine (IUPAC name) (640)+TX, phoxim (642)+TX,phoxim-methyl (1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX,pirimiphos-ethyl (1345)+TX, pirimiphos-methyl (652)+TX,polychlorodicyclopentadiene isomers (IUPAC name) (1346)+TX,polychloroterpenes (traditional name) (1347)+TX, potassium arsenite[CCN]+TX, potassium thiocyanate [CCN]+TX, prallethrin (655)+TX,precocene I (alternative name) [CCN]+TX, precocene II (alternative name)[CCN]+TX, precocene III (alternative name) [CCN]+TX, primidophos(1349)+TX, profenofos (662)+TX, profluthrin [CCN]+TX, promacyl(1354)+TX, promecarb (1355)+TX, propaphos (1356)+TX, propetamphos(673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothiofos(686)+TX, prothoate (1362)+TX, protrifenbute [CCN]+TX, pymetrozine(688)+TX, pyraclofos (689)+TX, pyrazophos (693)+TX, pyresmethrin(1367)+TX, pyrethrin 1 (696)+TX, pyrethrin II (696)+TX, pyrethrins(696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, pyriproxyfen(708)+TX, quassia (alternative name) [CCN]+TX, quinalphos (711)+TX,quinalphos-methyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX,R-1492 (development code) (1382)+TX, rafoxanide (alternative name)[CCN]+TX, resmethrin (719)+TX, rotenone (722)+TX, RU 15525 (developmentcode) (723)+TX, RU 25475 (development code) (1386)+TX, ryania(alternative name) (1387)+TX, ryanodine (traditional name) (1387)+TX,sabadilla (alternative name) (725)+TX, schradan (1389)+TX, sebufos(alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009(compound code)+TX, SI-0205 (compound code)+TX, SI-0404 (compoundcode)+TX, SI-0405 (compound code)+TX, silafluofen (728)+TX, SN 72129(development code) (1397)+TX, sodium arsenite [CCN]+TX, sodium cyanide(444)+TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399)+TX,sodium hexafluorosilicate (1400)+TX, sodium pentachlorophenoxide(623)+TX, sodium selenate (IUPAC name) (1401)+TX, sodium thiocyanate[CCN]+TX, sophamide (1402)+TX, spinosad (737)+TX, spiromesifen (739)+TX,spirotetrmat (CCN)+TX, sulcofuron (746)+TX, sulcofuron-sodium (746)+TX,sulfluramid (750)+TX, sulfotep (753)+TX, sulfuryl fluoride (756)+TX,sulprofos (1408)+TX, tar oils (alternative name) (758)+TX,tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX,tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos (764)+TX,teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos (770)+TX, TEPP(1417)+TX, terallethrin (1418)+TX, terbam (alternative name)+TX,terbufos (773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos(777)+TX, tetramethrin (787)+TX, theta-cypermethrin (204)+TX,thiacloprid (791)+TX, thiafenox (alternative name)+TX, thiamethoxam(792)+TX, thicrofos (1428)+TX, thiocarboxime (1431)+TX, thiocyclam(798)+TX, thiocyclam hydrogen oxalate (798)+TX, thiodicarb (799)+TX,thiofanox (800)+TX, thiometon (801)+TX, thionazin (1434)+TX, thiosultap(803)+TX, thiosultap-sodium (803)+TX, thuringiensin (alternative name)[CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin(813)+TX, transpermethrin (1440)+TX, triamiphos (1441)+TX, triazamate(818)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,trichlorfon (824)+TX, trichlormetaphos-3 (alternative name) [CCN]+TX,trichloronat (1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX,trimethacarb (840)+TX, triprene (1459)+TX, vamidothion (847)+TX,vaniliprole [CCN]+TX, veratridine (alternative name) (725)+TX, veratrine(alternative name) (725)+TX, XMC (853)+TX, xylylcarb (854)+TX, YI-5302(compound code)+TX, zeta-cypermethrin (205)+TX, zetamethrin (alternativename)+TX, zinc phosphide (640)+TX, zolaprofos (1469) and ZXI 8901(development code) (858)+TX, cyantraniliprole [736994-63-19+TX,chlorantraniliprole [500008-45-7]+TX, cyenopyrafen [560121-52-0]+TX,cyflumetofen [400882-07-7]+TX, pyrifluquinazon [337458-27-2]+TX,spinetoram [187166-40-1+187166-15-0]+TX, spirotetramat [203313-25-1]+TX,sulfoxaflor [946578-00-3]+TX, flufiprole [704886-18-0]+TX, meperfluthrin[915288-13-0]+TX, tetramethylfluthrin [84937-88-2]+TX, triflumezopyrim(disclosed in WO 2012/092115)+TX, fluxametamide (WO 2007/026965)+TX,epsilon-metofluthrin [240494-71-7]+TX, epsilon-momfluorothrin[1065124-65-3]+TX, fluazaindolizine [1254304-22-7]+TX, chloroprallethrin[399572-87-3]+TX, fluxametamide [928783-29-3]+TX, cyhalodiamide[1262605-53-7]+TX, tioxazafen [330459-31-9]+TX, broflanilide[1207727-04-5]+TX, flufiprole [704886-18-0]+TX, cyclaniliprole[1031756-98-5]+TX, tetraniliprole [1229654-66-3]+TX, guadipyr (describedin WO2010/060231)+TX, cycloxaprid (described in WO 2005/077934)+TX,spiropidion+TX, Afidopyropen+TX, flupyrimin+TX, Momfluorothrin+TX,kappa-bifenthrin+TX, kappa-tefluthrin+TX, Dichloromezotiaz+TX,Tetrachloraniliprole+TX, benzpyrimoxan+TX;

a molluscicide selected from the group of substances consisting ofbis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX,calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite[CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate(IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX,niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol(623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX,thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX,trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) andtriphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole[394730-71-3]+TX, a nematicide selected from the group of substancesconsisting of AKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane(IUPAC/Chemical Abstracts name) (1045)+TX, 1,2-dichloropropane(IUPAC/Chemical Abstracts name) (1062)+TX, 1,2-dichloropropane with1,3-dichloropropene (IUPAC name) (1063)+TX, 1,3-dichloropropene(233)+TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/ChemicalAbstracts name) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPACname) (980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid(IUPAC name) (1286)+TX, 6-isopentenylaminopurine (alternative name)(210)+TX, abamectin (1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX,aldicarb (16)+TX, aldoxycarb (863)+TX, AZ 60541 (compound code)+TX,benclothiaz [CCN]+TX, benomyl (62)+TX, butylpyridaben (alternativename)+TX, cadusafos (109)+TX, carbofuran (118)+TX, carbon disulfide(945)+TX, carbosulfan (119)+TX, chloropicrin (141)+TX, chlorpyrifos(145)+TX, cloethocarb (999)+TX, cytokinins (alternative name) (210)+TX,dazomet (216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX,dichlofenthion (1051)+TX, dicliphos (alternative name)+TX, dimethoate(262)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX,emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX,ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX,fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fosthiazate(408)+TX, fosthietan (1196)+TX, furfural (alternative name) [CCN]+TX,GY-81 (development code) (423)+TX, heterophos [CCN]+TX, iodomethane(IUPAC name) (542)+TX, isamidofos (1230)+TX, isazofos (1231)+TX,ivermectin (alternative name) [CCN]+TX, kinetin (alternative name)(210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium(alternative name) (519)+TX, metam-sodium (519)+TX, methyl bromide(537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime (alternativename) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, Myrotheciumverrucaria composition (alternative name) (565)+TX, NC-184 (compoundcode)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX,phosphocarb [CCN]+TX, sebufos (alternative name)+TX, selamectin(alternative name) [CCN]+TX, spinosad (737)+TX, terbam (alternativename)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/ChemicalAbstracts name) (1422)+TX, thiafenox (alternative name)+TX, thionazin(1434)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,xylenols [CCN]+TX, YI-5302 (compound code) and zeatin (alternative name)(210)+TX, fluensulfone [318290-98-1]+TX, fluopyram+TX,

a nitrification inhibitor selected from the group of substancesconsisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,

a plant activator selected from the group of substances consisting ofacibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) andReynoutria sachalinensis extract (alternative name) (720)+TX,

a rodenticide selected from the group of substances consisting of2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu(880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX,bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX,bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX,chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX,coumachlor (1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX,crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX,diphacinone (273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX,fluoroacetamide (379)+TX, flupropadine (1183)+TX, flupropadinehydrochloride (1183)+TX, gamma-HCH (430)+TX, HCH (430)+TX, hydrogencyanide (444)+TX, iodomethane (IUPAC name) (542)+TX, lindane (430)+TX,magnesium phosphide (IUPAC name) (640)+TX, methyl bromide (537)+TX,norbormide (1318)+TX, phosacetim (1336)+TX, phosphine (IUPAC name)(640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite[CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, sodium arsenite[CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX,strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zincphosphide (640)+TX,

a synergist selected from the group of substances consisting of2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934)+TX,5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX,farnesol with nerolidol (alternative name) (324)+TX, MB-599 (developmentcode) (498)+TX, MGK 264 (development code) (296)+TX, piperonyl butoxide(649)+TX, piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (developmentcode) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide(1406)+TX,

an animal repellent selected from the group of substances consisting ofanthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX,copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene(chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates(422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX,thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram(856)+TX,

a virucide selected from the group of substances consisting of imanin(alternative name) [CCN] and ribavirin (alternative name) [CCN]+TX,

a wound protectant selected from the group of substances consisting ofmercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl(802)+TX,

and biologically active compounds selected from the group of substancesconsisting of azaconazole (60207-31-0]+TX, bitertanol [70585-36-3]+TX,bromuconazole [116255-48-2]+TX, cyproconazole [94361-06-5]+TX,difenoconazole [119446-68-3]+TX, diniconazole [83657-24-3]+TX,epoxiconazole [106325-08-0]+TX, fenbuconazole [114369-43-6]+TX,fluquinconazole [136426-54-5]+TX, flusilazole [85509-19-9]+TX,flutriafol [76674-21-0]+TX, hexaconazole [79983-71-4]+TX, imazalil[35554-44-0]+TX, imibenconazole [86598-92-7]+TX, ipconazole[125225-28-7]+TX, metconazole [125116-23-6]+TX, myclobutanil[88671-89-0]+TX, pefurazoate [101903-30-4]+TX, penconazole[66246-88-6]+TX, prothioconazole [178928-70-6]+TX, pyrifenox[88283-41-4]+TX, prochloraz [67747-09-5]+TX, propiconazole[60207-90-1]+TX, simeconazole [149508-90-7]+TX, tebuconazole[107534-96-3]+TX, tetraconazole [112281-77-3]+TX, triadimefon[43121-43-3]+TX, triadimenol [55219-65-3]+TX, triflumizole[99387-89-0]+TX, triticonazole [131983-72-7]+TX, ancymidol[12771-68-5]+TX, fenarimol [60168-88-9]+TX, nuarimol [63284-71-9]+TX,bupirimate [41483-43-6]+TX, dimethirimol [5221-53-4]+TX, ethirimol[23947-60-6]+TX, dodemorph [1593-77-7]+TX, fenpropidine [67306-00-7]+TX,fenpropimorph [67564-91-4]+TX, spiroxamine [118134-30-8]+TX, tridemorph[81412-43-3]+TX, cyprodinil [121552-61-2]+TX, mepanipyrim[110235-47-7]+TX, pyrimethanil [53112-28-0]+TX, fenpiclonil[74738-17-3]+TX, fludioxonil [131341-86-1]+TX, benalaxyl[71626-11-4]+TX, furalaxyl [57646-30-7]+TX, metalaxyl [57837-19-1]+TX,R-metalaxyl [70630-17-0]+TX, ofurace [58810-48-3]+TX, oxadixyl[77732-09-3]+TX, benomyl [17804-35-2]+TX, carbendazim [10605-21-7]+TX,debacarb [62732-91-6]+TX, fuberidazole [3878-19-1]+TX, thiabendazole[148-79-8]+TX, chlozolinate [84332-86-5]+TX, dichlozoline[24201-58-9]+TX, iprodione [36734-19-7]+TX, myclozoline [54864-61-8]+TX,procymidone [32809-16-8]+TX, vinclozoline [50471-44-8]+TX, boscalid[188425-85-6]+TX, carboxin [5234-68-4]+TX, fenfuram [24691-80-3]+TX,flutolanil [66332-96-5]+TX, mepronil [55814-41-0]+TX, oxycarboxin[5259-88-1]+TX, penthiopyrad [183675-82-3]+TX, thifluzamide[130000-40-7]+TX, guazatine [108173-90-6]+TX, dodine [2439-10-3][112-65-2] (free base)+TX, iminoctadine [13516-27-3]+TX, azoxystrobin[131860-33-8]+TX, dimoxystrobin [149961-52-4]+TX, enestroburin {Proc.BCPC, Int. Congr., Glasgow, 2003, 1, 93}+TX, fluoxastrobin[361377-29-9]+TX, kresoxim-methyl [143390-89-0]+TX, metominostrobin[133408-50-1]+TX, trifloxystrobin [141517-21-7]+TX, orysastrobin[248593-16-0]+TX, picoxystrobin [117428-22-5]+TX, pyraclostrobin[175013-18-0]+TX, ferbam [14484-64-1]+TX, mancozeb [8018-01-7]+TX, maneb[12427-38-2]+TX, metiram [9006-42-2]+TX, propineb [12071-83-9]+TX,thiram [137-26-8]+TX, zineb [12122-67-7]+TX, ziram [137-30-4]+TX,captafol [2425-06-1]+TX, captan [133-06-2]+TX, dichlofluanid[1085-98-9]+TX, fluoroimide [41205-21-4]+TX, folpet [133-07-3]+TX,tolylfluanid [731-27-1]+TX, bordeaux mixture [8011-63-0]+TX,copperhydroxid [20427-59-2]+TX, copperoxychlorid [1332-40-7]+TX,coppersulfat [7758-98-7]+TX, copperoxid [1317-39-1]+TX, mancopper[53988-93-5]+TX, oxine-copper [10380-28-6]+TX, dinocap [131-72-6]+TX,nitrothal-isopropyl [10552-74-6]+TX, edifenphos [17109-49-8]+TX,iprobenphos [26087-47-8]+TX, isoprothiolane [50512-35-1]+TX, phosdiphen[36519-00-3]+TX, pyrazophos [13457-18-6]+TX, tolclofos-methyl[57018-04-9]+TX, acibenzolar-S-methyl [135158-54-2]+TX, anilazine[101-05-3]+TX, benthiavalicarb [413615-35-7]+TX, blasticidin-S[2079-00-7]+TX, chinomethionat [2439-01-2]+TX, chloroneb [2675-77-6]+TX,chlorothalonil [1897-45-6]+TX, cyflufenamid [180409-60-3]+TX, cymoxanil[57966-95-7]+TX, dichlone [117-80-6]+TX, diclocymet [139920-32-4]+TX,diclomezine [62865-36-5]+TX, dicloran [99-30-9]+TX, diethofencarb[87130-20-9]+TX, dimethomorph [110488-70-5]+TX, SYP-LI90 (Flumorph)[211867-47-9]+TX, dithianon [3347-22-6]+TX, ethaboxam [162650-77-3]+TX,etridiazole [2593-15-9]+TX, famoxadone [131807-57-3]+7X, fenamidone[161326-34-7]+TX, fenoxanil [115852-48-7]4+TX, fentin [668-34-8]+TX,ferimzone [89269-64-7]+TX, fluazinam [79622-59-6]+TX, fluopicolide[239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenhexamid[126833-17-8]+TX, fosetyl-aluminium [39148-24-8]+TX, hymexazol[10004-44-1]+TX, iprovalicarb [140923-17-7]+TX, IKF-916 (Cyazofamid)[120116-88-3]+TX, kasugamycin [6980-18-3]+TX, methasulfocarb[66952-49-6]+TX, metrafenone [220899-03-6]+TX, pencycuron[66063-05-6]+TX, phthalide [27355-22-2]+TX, polyoxins [11113-80-7]+TX,probenazole [27605-76-1]+TX, propamocarb [25606-41-1]+TX, proquinazid[189278-12-4]+TX, pyroquilon [57369-32-1]+TX, quinoxyfen[124495-18-7]+TX, quintozene [82-68-8]+TX, sulfur [7704-34-9]+TX,tiadinil [223580-51-6]+TX, triazoxide [72459-58-6]+TX, tricyclazole[41814-78-2]+TX, triforine [26644-46-2]+TX, validamycin [37248-47-8]+TX,zoxamide (RH7281) [156052-68-5]+TX, mandipropamid [374726-62-2]+TX,isopyrazam [881685-58-1]+TX, sedaxane [874967-67-6]+TX,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide(disclosed in WO 2007/048556)+TX,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(3′,4′,5′-trifluoro-biphenyl-2-yl)-amide (disclosed in WO2006/087343)+TX,[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11Hnaphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate[915972-17-7]+TX and1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide[926914-55-8]+TX, lancotrione [1486617-21-3]+TX, florpyrauxifen[943832-81-3]+TX, ipfentrifluconazole[1417782-08-1]+TX,mefentrifluconazole [1417782-03-6]+TX, quinofumelin [861647-84-9]+TX,chloroprallethrin [399572-87-3]+TX, cyhalodiamide [1262605-53-7]+TX,fluazaindolizine [1254304-22-7]+TX, fluxametamide [928783-29-3]+TX,epsilon-metofluthrin [240494-71-7]+TX, epsilon-momfluorothrin[1065124-65-3]+TX, pydiflumetofen [1228284-64-7]+TX, kappa-bifenthrin[439680-76-9]+TX, broflanilide [1207727-04-5]+TX, dicloromezotiaz[1263629-39-5]+TX, dipymetitrone [16114-35-5]+TX, pyraziflumid[942515-63-1]+TX and kappa-tefluthrin [391634-71-2]+TX, fenpicoxamid[517875-34-2]+TX; flufenpyrrolidone+TX, benzpyrimoxan [1449021-97-9]+TX;isocycloseram+TX, rescalure [64309-03-1]+TX; aminopyrifen[1531626-08-0]+TX; and microbials including: Acinetobacter lwoffii+TX,Acremonium alternatum+TX+TX, Acremonium cephalosporium+TX+TX, Acremoniumdiospyri+TX, Acremonium obclavatum+TX, Adoxophyes orana granulovirus(AdoxGV) (Capex®)+TX, Agrobacterium radiobacter strain K84(Galltrol-A®)+TX, Alternaria alternate+TX, Alternaria cassia+TX,Alternaria destruens (Smolder®)+TX, Ampelomyces quisqualis (AQ10®)+TX,Aspergillus flavus AF36 (AF36®)+TX, Aspergillus flavus NRRL 21882(Aflaguard®)+TX, Aspergillus spp.+TX, Aureobasidium pullulans+TX,Azospirillum+TX, (MicroAZ®+TX, TAZO B®)+TX, Azotobacter+TX, Azotobacterchroocuccum (Azotomeal®)+TX, Azotobacter cysts (Bionatural BloomingBlossoms®)+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX,Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strainAQ746+TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®)+TX,Bacillus licheniformis strain 3086 (EcoGuard®+TX, Green Releaf®)+TX,Bacillus circulans+TX, Bacillus firmus (BioSafe®+TX, BioNem-WP®+TX,VOTiVO®)+TX, Bacillus firmus strain 1-1582+TX, Bacillus macerans+TX,Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoidesstrain AQ726+TX, Bacillus papillae (Milky Spore Powder®)+TX, Bacilluspumilus spp.+TX, Bacillus pumilus strain GB34 (Yield Shield®)+TX,Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808(Sonata®+TX, Ballad Plus®)+TX, Bacillus spahericus (VectoLex®)+TX,Bacillus spp.+TX, Bacillus spp. strain AQ175+TX, Bacillus spp. strainAQ177+TX, Bacillus spp. strain AQ178+TX, Bacillus subtilis strain QST713 (CEASE®+TX, Serenade®+TX, Rhapsody®)+TX, Bacillus subtilis strainQST 714 (JAZZ®)+TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilisstrain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilisstrain QST3004+TX, Bacillus subtilis var. amyloliquefaciens strain FZB24(Taegro®+TX, Rhizopro®)+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillusthuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91(Agree®)+TX, Bacillus thuringiensis israelensis (BMP123®+TX,Aquabac®+TX, VectoBac®)+TX, Bacillus thuringiensis kurstaki(Javelin®+TX, Deliver®+TX, CryMax®+TX, Bonide®+TX, Scutella WP®+TX,Turilav WP®+TX, Astuto®+TX, Dipel WP®+TX, Biobit®+TX, Foray®)+TX,Bacillus thuringiensis kurstaki BMP 123 (Baritone®)+TX, Bacillusthuringiensis kurstaki HD-1 (Bioprotec-CAF/3P®)+TX, Bacillusthuringiensis strain BD #32+TX, Bacillus thuringiensis strain AQ52+TX,Bacillus thuringiensis var. aizawai (XenTari®+TX, DiPel®)+TX, bacteriaspp. (GROWMEND®+TX, GROWSWEET®+TX, Shootup®)+TX, bacteriophage ofClavipacter michiganensis (AgriPhage®)+TX, Bakflor®+TX, Beauveriabassiana (Beaugenic®+TX, Brocaril WP®)+TX, Beauveria bassiana GHA(Mycotrol ES® +TX, Mycotrol O®+TX, BotaniGuard®)+TX, Beauveriabrongniartii (Engerlingspilz®+TX, Schweizer Beauveria®+TX,Melocont®)+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobiumjaponicum (TerraMax®)+TX, Brevibacillus brevis+TX, Bacillusthuringiensis tenebrionis (Novodor®)+TX, BtBooster+TX, Burkholderiacepacia (Deny®+TX, Intercept®+TX, Blue Circle®)+TX, Burkholderiagladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadianthistle fungus (CBH Canadian Bioherbicide®)+TX, Candida butyri+TX,Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candidaguilliermondii+TX, Candida melibiosica+TX, Candida oleophila strainO+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candidapulcherrima+TX, Candida reukaufii+TX, Candida saitoana (Bio-Coat®+TX,Biocure®)+TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX,Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes(Nova-Cide®)+TX, Chaetomium globosum (Nova-Cide®)+TX, Chromobacteriumsubtsugae strain PRAA4-1T (Grandevo®)+TX, Cladosporiumcladosporioides+TX, Cladosporium oxysporum+TX, Cladosporiumchlorocephalum+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX,Clonostachys rosea (EndoFine®)+TX, Colletotrichum acutatum+TX,Coniothyrium minitans (Cotans WG®)+TX, Coniothyrium spp.+TX,Cryptococcus albidus (YIELDPLUS®)+TX, Cryptococcus humicola+TX,Cryptococcus infirmo-miniatus+TX, Cryptococcus laurentii+TX,Cryptophlebia leucotreta granulovirus (Cryptex®)+TX, Cupriaviduscampinensis+TX, Cydia pomonella granulovirus (CYD-X®)+TX, Cydiapomonella granulovirus (Madex®+TX, Madex Plus®+TX, MadexMax/Carpovirusine®)+TX, Cylindrobasidium laeve (Stumpout®)+TX,Cylindrocladium+TX, Debaryomyces hansenii4+TX, Drechslerahawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX,Entomophtora virulenta (Vektor®)+TX, Epicoccum nigrum+TX, Epicoccumpurpurascens+TX, Epicoccum spp.+TX, Filobasidium floriforme+TX, Fusariumacuminatum+TX, Fusarium chlamydosporum+TX, Fusarium oxysporum(Fusaclean®/Biofox C®)+TX, Fusarium proliferatum+TX, Fusarium spp.+TX,Galactomyces geotrichum+TX, Gliocladium catenulatum (Primastop®+TX,Prestop®)+TX, Gliocladium roseum+TX, Gliocladium spp. (SoilGard®)+TX,Gliocladium virens (Soilgard®)+TX, Granulovirus (Granupom®)+TX,Halobacillus halophilus+TX, Halobacillus litoralis+TX, Halobacillustrueperi+TX, Halomonas spp.+TX, Halomonas subglaciescola+TX, Halovibriovariabilis+TX, Hanseniaspora uvarum+TX, Helicoverpa armigeranucleopolyhedrovirus (Helicovex®)+TX, Helicoverpa zea nuclearpolyhedrosis virus (Gemstar®)+TX, Isoflavone-formononetin(Myconate®)+TX, Kloeckera apiculata+TX, Kloeckera spp.+TX, Lagenidiumgiganteum (Laginex®)+TX, Lecanicillium longisporum (Vertiblast®)+TX,Lecanicillium muscarium (Vertikil®)+TX, Lymantria Disparnucleopolyhedrosis virus (Disparvirus®)+TX, Marinococcus halophilus+TX,Meira geulakonigii+TX, Metarhizium anisopliae (Met52®)+TX, Metarhiziumanisopliae (Destruxin WP®)+TX, Metschnikowia fruticola (Shemer®)+TX,Metschnikowia pulcherrima+TX, Microdochium dimerum (Antibot®)+TX,Micromonospora coerulea+TX, Microsphaeropsis ochracea+TX, Muscodor albus620 (Muscudor®)+TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp.(AMykor®+TX, Root Maximizer®)+TX, Myrothecium verrucaria strainAARC-0255 (DiTera®)+TX, BROS PLUS®+TX, Ophiostoma piliferum strain D97(Sylvanex®)+TX, Paecilomyces farinosus+TX, Paecilomyces fumosoroseus(PFR-97®+TX, PreFeRal®)+TX, Paecilomyces linacinus (Biostat WP®)+TX,Paecilomyces lilacinus strain 251 (MeloCon WG®)+TX, Paenibacilluspolymyxa+TX, Pantoea agglomerans (BlightBan C9-1®)+TX, Pantoea spp.+TX,Pasteuria spp. (Econem®)+TX, Pasteuria nishizawae+TX, Penicilliumaurantiogriseum+TX, Penicillium billai (Jumpstart®+TX, TagTeam®)+TX,Penicillium brevicompactum+TX, Penicillium frequentans+TX, Penicilliumgriseofulvum+TX, Penicillium purpurogenum+TX, Penicillium spp.+TX,Penicillium viridicatum+TX, Phlebiopsis gigantean (Rotstop®)+TX,phosphate solubilizing bacteria (Phosphomeal®)+TX, Phytophthoracryptogea+TX, Phytophthora palmivora (Devine®)+TX, Pichia anomala+TX,Pichia guilermondii+TX, Pichia membranaefaciens+TX, Pichia onychis+TX,Pichia stipites+TX, Pseudomonas aeruginosa+TX, Pseudomonas aureofasciens(Spot-Less Biofungicide®)+TX, Pseudomonas cepacia+TX, Pseudomonaschlororaphis (AtEze®)+TX, Pseudomonas corrugate+TX, Pseudomonasfluorescens strain A506 (BlightBan A506®)+TX, Pseudomonas putida+TX,Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae(Bio-Save®)+TX, Pseudomonas viridiflava+TX, Pseudomonas fluorescens(Zequanox®)+TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®)+TX,Puccinia canaliculata+TX, Puccinia thlaspeos (Wood Warrior®)+TX, Pythiumparoecandrum+TX, Pythium oligandrum (Polygandron®+TX, Polyversum®)+TX,Pythium periplocum+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia(Dormal®+TX, Vault®)+TX, Rhizoctonia+TX, Rhodococcus globerulus strainAQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX,Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX,Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomycescerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotiniaminor (SARRITOR®)+TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX,Spodoptera exigua nuclear polyhedrosis virus (Spod-X®+TX, Spexit®)+TX,Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX,Sordaria fimicola+TX, Spodoptera littoralis nucleopolyhedrovirus(Littovir®)+TX, Sporobolomyces roseus+TX, Stenotrophomonasmaltophilia+TX, Streptomyces ahygroscopicus+TX, Streptomycesalbaduncus+TX, Streptomyces exfoliates+TX, Streptomyces galbus+TX,Streptomyces griseoplanus+TX, Streptomyces griseoviridis (Mycostop®)+TX,Streptomyces lydicus (Actinovate®)+TX, Streptomyces lydicus WYEC-108(ActinoGrow®)+TX, Streptomyces violaceus+TX, Tilletiopsis minor4+TX,Tilletiopsis spp.+TX, Trichoderma asperellum (T34 Biocontrol®)+TX,Trichoderma gamsii (Tenet®)+TX, Trichoderma atroviride (Plantmate®)+TX,Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai(Mycostar®)+TX, Trichoderma harzianum T-22 (Trianum-P®+TX, PlantShieldHC®+TX, RootShield®+TX, Trianum-G®)+TX, Trichoderma harzianum T-39(Trichodex®)+TX, Trichoderma inhamatum+TX, Trichoderma koningii+TX,Trichoderma spp. LC 52 (Sentinel®)+TX, Trichoderma lignorum+TX,Trichoderma longibrachiatum+TX, Trichoderma polysporum (Binab T®)+TX,Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerlyGliocladium virens GL-21) (SoilGuard®)+TX, Trichoderma viride+TX,Trichoderma viride strain ICC 080 (Remedier®)+TX, Trichosporonpullulans+TX, Trichosporon spp.+TX, Trichothecium spp.+TX, Trichotheciumroseum+TX, Typhula phacorrhiza strain 94670+TX, Typhula phacorrhizastrain 94671+TX, Ulocladium atrum+TX, Ulocladium oudemansii(Botry-Zen®)+TX, Ustilago maydis+TX, various bacteria and supplementarymicronutrients (Natural II®)+TX, various fungi (MillenniumMicrobes®)+TX, Verticillium chlamydosporium+TX, Verticillium lecanii(Mycotal®+TX, Vertalec®)+TX, Vip3Aa20 (VlPtera®)+TX, Virgibaclillusmarismortui+TX, Xanthomonas campestris pv. Poae (Camperico®)+TX,Xenorhabdus bovienii+TX, Xenorhabdus nematophilus; and

Plant extracts including: pine oil (Retenol®)+TX, azadirachtin (PlasmaNeem Oil®+TX, AzaGuard®+TX, MeemAzal®+TX, Molt-X®+TX, Botanical IGR(Neemazad®+TX, Neemix®)+TX, canola oil (Lilly Miller Vegol®)+TX,Chenopodium ambrosioides near ambrosioides (Requiem®)+TX, Chrysanthemumextract (Crisant®)+TX, extract of neem oil (Trilogy®)+TX, essentialsoils of Labiatae (Botania®)+TX, extracts of clove rosemary peppermintand thyme oil (Garden insect Killer®)+TX, Glycinebetaine(Greenstim®)+TX, garlic+TX, lemongrass oil (GreenMatch®)+TX, neemoil+TX, Nepeta cataria (Catnip oil)+TX, Nepeta catarina+TX, nicotine+TX,oregano oil (MossBuster®)+TX, Pedaliaceae oil (Nematon®)+TX,pyrethrum+TX, Quillaja saponaria (NemaQ®)+TX, Reynoutria sachalinensis(Regalia®+TX, Sakalia®)+TX, rotenone (Eco Roten®)+TX, Rutaceae plantextract (Soleo®)+TX, soybean oil (Ortho Ecosense®)+TX, tea tree oil(Timorex Gold®)+TX, thymus oil+TX, AGNIQUE® MMF+TX, BugOil®+TX, mixtureof rosemary sesame pepermint thyme and cinnamon extracts (EF 300®)+TX,mixture of clove rosemary and peppermint extract (EF 400®)+TX, mixtureof clove pepermint garlic oil and mint (Soil Shot®)+TX, kaolin(Screen®)+TX, storage glucam of brown algae (Laminarin®); and

pheromones including: blackheaded fireworm pheromone (3M SprayableBlackheaded Fireworm Pheromone®)+TX, Codling Moth Pheromone (Paramountdispenser-(CM)/Isomate C-Plus®)+TX, Grape Berry Moth Pheromone (3MMEC-GBM Sprayable Pheromone®)+TX, Leafroller pheromone (3M MEC-LRSprayable Pheromone®)+TX, Muscamone (Snip7 Fly Bait®+TX, Starbar PremiumFly Bait®)+TX, Oriental Fruit Moth Pheromone (3M oriental fruit mothsprayable Pheromone®)+TX, Peachtree Borer Pheromone (Isomate-P®)+TX,Tomato Pinworm Pheromone (3M Sprayable Pheromone®)+TX, Entostat powder(extract from palm tree) (Exosex CM®)+TX, (E+TX,Z+TX,Z)-3+TX,8+TX,11Tetradecatrienyl acetate+TX,(Z+TX,Z+TX,E)-7+TX,11+TX,13-Hexadecatrienal+TX,(E+TX,Z)-7+TX,9-Dodecadien-1-yl acetate+TX, 2-Methyl-1-butanol+TX,Calcium acetate+TX, Scenturion®+TX, Biolure®+TX, Check-Mate®+TX,Lavandulyl senecioate; and

Macrobials including: Aphelinus abdominalis+TX, Aphidius ervi(Aphelinus-System®)+TX, Acerophagus papaya+TX, Adalia bipunctata(Adalia-System®)+TX, Adalia bipunctata (Adaline®)+TX, Adalia bipunctata(Aphidalia®)+TX, Ageniaspis citricola+TX, Ageniaspis fuscicollis+TX,Amblyseius andersoni (Anderline®+TX, Andersoni-System®)+TX, Amblyseiuscalifornicus (Amblyline®+TX, Spical®)+TX, Amblyseius cucumeris(Thripex®+TX, Bugline Cucumeris®)+TX, Amblyseius fallacis(Fallacis®)+TX, Amblyseius swirskii (Bugline Swirskii®+TX,Swirskii-Mite®)+TX, Amblyseius womersleyi (WomerMite®)+TX, Amitushesperidum+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX, Anagyruskamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci (Citripar®)+TX,Anicetus benefices+TX, Anisopteromalus calandrae+TX, Anthocorisnemoralis (Anthocoris-System®)+TX, Aphelinus abdominalis (Apheline®+TX,Aphiline®)+TX, Aphelinus asychis+TX, Aphidius colemani (Aphipar®)+TX,Aphidius ervi (Ervipar®)+TX, Aphidius gifuensis+TX, Aphidius matricariae(Aphipar-M®)+TX, Aphidoletes aphidimyza (Aphidend®)+TX, Aphidoletesaphidimyza (Aphidoline®)+TX, Aphytis lingnanensis+TX, Aphytismelinus+TX, Aprostocetus hagenowii+TX, Atheta coriaria (Staphyline®)+TX,Bombus spp.+TX, Bombus terrestris (Natupol Beehive®)+TX, Bombusterrestris (Beeline®+TX, Tripol®)+TX, Cephalonomia stephanoderis+TX,Chilocorus nigritus+TX, Chrysoperla carnea (Chrysoline®)+TX, Chrysoperlacarnea (Chrysopa®)+TX, Chrysoperla rufilabris+TX, Cirrospilusingenuus+TX, Cirrospilus quadristriatus+TX, Citrostichusphyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus spp.+TX,Coccidoxenoides perminutus (Planopar®)+TX, Coccophagus cowperi+TX,Coccophagus lycimnia+TX, Cotesia flavipes+TX, Cotesia plutellae+TX,Cryptolaemus montrouzieri (Cryptobug®+TX, Cryptoline®)+TX, Cybocephalusnipponicus+TX, Dacnusa sibirica+TX, Dacnusa sibirica (Minusa®)+TX,Diglyphus isaea (Diminex®)+TX, Delphastus catalinae (Delphastus®)+TX,Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Diachasmimorphalongicaudata+TX, Diaparsis jucunda+TX, Diaphorencyrtus aligarhensis+TX,Diglyphus isaea+TX, Diglyphus isaea (Miglyphus®+TX, Digline®)+TX,Dacnusa sibirica (DacDigline®+TX, Minex®)+TX, Diversinervus spp.+TX,Encarsia citrina+TX, Encarsia formosa (Encarsia Max®+TX, Encarline®+TX,En-Strip®)+TX, Eretmocerus eremicus (Enermix®)+TX, Encarsiaguadeloupae+TX, Encarsia haitiensis+TX, Episyrphus balteatus(Syrphidend®)+TX, Eretmoceris siphonini+TX, Eretmocerus californicus+TX,Eretmocerus eremicus (Ercal®+TX, Eretline e®)+TX, Eretmocerus eremicus(Bemimix®)+TX, Eretmocerus hayati+TX, Eretmocerus mundus (Bemipar®+TX,Eretline m®)+TX, Eretmocerus siphonini4+TX, Exochomusquadripustulatus+TX, Feltiella acarisuga (Spidend®)+TX, Feltiellaacarisuga (Feltiline®)+TX, Fopius arisanus+TX, Fopius ceratitivorus+TX,Formononetin (Wirless Beehome®)+TX, Franklinothrips vespiformis(Vespop®)+TX, Galendromus occidentalis+TX, Goniozus legneri+TX,Habrobracon hebetor+TX, Harmonia axyridis (HarmoBeetle®)+TX,Heterorhabditis spp. (Lawn Patrol®)+TX, Heterorhabditis bacteriophora(NemaShield HB®+TX, Nemaseek®+TX, Terranem-Nam®+TX, Terranem®4+TX,Larvanem®+TX, B-Green®+TX, NemAttack®+TX, Nematop®)+TX, Heterorhabditismegidis (Nemasys H®+TX, BioNem H®+TX, Exhibitline hm®+TX,Larvanem-M®)+TX, Hippodamia convergens+TX, Hypoaspis aculeifer(Aculeifer-System®+TX, Entomite-A®)+TX, Hypoaspis miles (Hypoline m®+TX,Entomite-M®)+TX, Lbalia leucospoides+TX, Lecanoideus floccissimus+TX,Lemophagus errabundus+TX, Leptomastidea abnormis+TX, Leptomastixdactylopii (Leptopar®)+TX, Leptomastix epona+TX, Lindorus lophanthae+TX,Lipolexis oregmae+TX, Lucilia caesar (Natufly®)+TX, Lysiphlebustestaceipes+TX, Macrolophus caliginosus (Mirical-N®+TX, Macroline c®+TX,Mirical®)+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycuslounsburyi+TX, Micromus angulatus (Milacewing®)+TX, Microterysflavus+TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®)+TX,Neodryinus typhlocybae+TX, Neoseiulus californicus+TX, Neoseiuluscucumeris (THRYPEX®)+TX, Neoseiulus fallacis+TX, Nesideocoris tenuis(NesidioBug®+TX, Nesibug®)+TX, Ophyra aenescens (Biofly®)+TX, Oriusinsidiosus (Thripor-1®+TX, Oriline i®)+TX, Orius laevigatus(Thripor-L®+TX, Oriline I®)+TX, Orius majusculus (Oriline m®)+TX, Oriusstrigicollis (Thripor-S®)+TX, Pauesia juniperorum+TX, Pediobiusfoveolatus+TX, Phasmarhabditis hermaphrodita (Nemaslug®)+TX,Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiuluspersimilis (Spidex®+TX, Phytoline p®)+TX, Podisus maculiventris(Podisus®)+TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX,Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastixmexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX,Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX,Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae(Ervibank®)+TX, Steinernema carpocapsae (Nematac C®+TX, Millenium®+TX,BioNem C®+TX, NemAttack®+TX, Nemastar®+TX, Capsanem®)+TX, Steinernemafeltiae (NemaShield®+TX, Nemasys F®+TX, BioNem F®+TX,Steinernema-System®+TX, NemAttack®+TX, Nemaplus®+TX, Exhibitline sf®+TX,Scia-Rid®+TX, Entonem®)+TX, Steinernema kraussei (Nemasys L®+TX, BioNemL®+TX, Exhibitline srb®)+TX, Steinernema riobrave (BioVector®+TX,BioVektor®)+TX, Steinernema scapterisci (Nematac S®)+TX, Steinernemaspp.+TX, Steinernematid spp. (Guardian Nematodes®)+TX, Stethoruspunctillum (Stethorus®)+TX, Tamarixia radiate+TX, Tetrastichussetifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogrammabrassicae (Tricholine b®)+TX, Trichogramma brassicae (Tricho-Strip®)+TX,Trichogramma evanescens+TX, Trichogramma minutum+TX, Trichogrammaostriniae+TX, Trichogramma platneri+TX, Trichogramma pretiosum+TX,Xanthopimpla stemmator; and

other biologicals including: abscisic acid+TX, bioSea®+TX,Chondrostereum purpureum (Chontrol Paste®)+TX, Colletotrichumgloeosporioides (Collego®)+TX, Copper Octanoate (Cueva®)+TX, Delta traps(Trapline d®)+TX, Erwinia amylovora (Harpin) (ProAct®+TX, Ni-HIBIT GoldCST®)+TX, Ferri-phosphate (Ferramol®)+TX, Funnel traps (Trapline y®)+TX,Gallex®+TX, Grower's Secret®+TX, Homo-brassonolide+TX, Iron Phosphate(Lilly Miller Worry Free Ferramol Slug & Snail Bait®)+TX, MCP hail trap(Trapline f®)+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris(Des-X®)+TX, BioGain®+TX, Aminomite®+TX, Zenox®+TX, Pheromone trap(Thripline ams®)+TX, potassium bicarbonate (MilStop®)+TX, potassiumsalts of fatty acids (Sanova®)+TX, potassium silicate solution(Sil-Matrix®)+TX, potassium iodide+potassiumthiocyanate (Enzicur®)+TX,SuffOil-X®+TX, Spider venom+TX, Nosema locustae (Semaspore OrganicGrasshopper Control®)+TX, Sticky traps (Trapline YF®+TX, RebellAmarillo®)+TX and Traps (Takitrapline y+b®)+TX;

or a biologically active compound or agent selected from:Brofluthrinate+TX, Diflovidazine+TX, Flometoquin+TX, Fluhexafon+TX,Plutella xylostella Granulosis virus+TX, Cydia pomonella Granulosisvirus+TX, Imicyafos+TX, Heliothis virescens Nucleopolyhedrovirus+TX,Heliothis punctigera Nucleopolyhedrovirus+TX, Helicoverpa zeaNucleopolyhedrovirus+TX, Spodoptera frugiperda Nucleopolyhedrovirus+TX,Plutella xylostella Nucleopolyhedrovirus+TX, p-cymene+TX,Pyflubumide+TX, Pyrafluprole+TX, QRD 420+TX, QRD 452+TX, QRD 460+TX,Terpenoid blends+TX, Terpenoids+TX, Tetraniliprole+TX, andα-terpinene+TX;

or an active substance referenced by a code+TX, such as code AE 1887196(BSC-BX60309)+TX, code NNI-0745 GR+TX, code IKI-3106+TX, codeJT-L001+TX, code ZNQ-08056+TX, code IPPA152201+TX, code HNPC-A9908 (CAS:[660411-21-2])+TX, code HNPC-A2005 (CAS: [860028-12-2])+TX, codeJS118+TX, code ZJ0967+TX, code ZJ2242+TX, code JS7119 (CAS:[929545-74-4])+TX, code SN-1172+TX, code HNPC-A9835+TX, codeHNPC-A9955+TX, code HNPC-A3061+TX, code Chuanhua 89-1+TX, codeIPP-10+TX, code ZJ3265+TX, code JS9117+TX, code ZJ3757+TX, codeZJ4042+TX, code ZJ4014+TX, code ITM-121+TX, code DPX-RAB55(DKI-2301)+TX, code NA-89+TX, code MIE-1209+TX, code MCI-8007+TX, codeBCS-CL73507+TX, code S-1871+TX, code DPX-RDS63+TX, code AKD-1193+TX;

or other biologically active compounds or agents selected from:Quinofumelin+TX, mefentrifluconazol+TX, fenpicoxamid+TX, fluindapyr+TX,inpyrfluxam+TX or indiflumetpyr+TX, isoflucypram+TX, pyrapropoyne+TX,florylpicoxamid+TX, metyltetraprole+TX, ipflufenoquin+TX,pyridachlometyl+TX or chlopyridiflu+TX, tetrachlorantraniliprole+TX,tetrachloraniliprole+TX, Tetflupyrolimet+TX, Triflufenpyrrolidone+TX,Tyclopyrazoflor+TX, flupyrimin+TX or pyrifluramide+TX, benzpyrimoxan+TX,beflubutamid-M+TX, Benzosufyl+TX or oxazosulfyl+TX, etpyrafen+TX,acynonapyr+TX or pyrinonafen+TX, oxotrione+TX, bixlozone+TX orclofendizone+TX or dicloroxizone+TX, cyclopyranil+TX orpyrazocyclonil+TX or cyclopyrazonil+TX, alpha-bromadiolone+TX,Oxathiapiprolin+TX, Fluopyram+TX, Penflufen+TX, Fluoxopyrosad+TX,fluoxapiprolin+TX and Flupyradifurone+TX.

The references in brackets behind the active ingredients, e.g.[3878-19-1] refer to the Chemical Abstracts Registry number. The abovedescribed mixing partners are known. Where the active ingredients areincluded in “The Pesticide Manual” [The Pesticide Manual—A WorldCompendium; Thirteenth Edition; Editor: C. D. S. TomLin; The BritishCrop Protection Council], they are described therein under the entrynumber given in round brackets hereinabove for the particular compound;for example, the compound “abamectin” is described under entry number(1). Where “[CCN]” is added hereinabove to the particular compound, thecompound in question is included in the “Compendium of Pesticide CommonNames”, which is accessible on the internet [A. Wood; Compendium ofPesticide Common Names, Copyright © 1995-2004]; for example, thecompound “acetoprole” is described under the internet addresshttp://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred tohereinabove by a so-called “common name”, the relevant “ISO common name”or another “common name” being used in individual cases. If thedesignation is not a “common name”, the nature of the designation usedinstead is given in round brackets for the particular compound; in thatcase, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemicalname”, a “traditional name”, a “compound name” or a “develoment code” isused or, if neither one of those designations nor a “common name” isused, an “alternative name” is employed. “CAS Reg. No” means theChemical Abstracts Registry Number.

The active ingredient mixture of the compounds of formula I selectedfrom Tables Y-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 and TableP with active ingredients described above comprises a compound selectedfrom Tables Y-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 and TableP and an active ingredient as described above preferably in a mixingratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, moreespecially in a ratio of from 20:1 to 1:20, even more especially from10:1 to 1:10, very especially from 5:1 and 1:5, special preference beinggiven to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2,or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5,or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2,or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.

The mixtures as described above can be used in a method for controllingpests, which comprises applying a composition comprising a mixture asdescribed above to the pests or their environment, with the exception ofa method for treatment of the human or animal body by surgery or therapyand diagnostic methods practised on the human or animal body.

The mixtures comprising a compound of formula I selected from Tables Y-1to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 and Table P and one ormore active ingredients as described above can be applied, for example,in a single “ready-mix” form, in a combined spray mixture composed fromseparate formulations of the single active ingredient components, suchas a “tank-mix”, and in a combined use of the single active ingredientswhen applied in a sequential manner, i.e. one after the other with areasonably short period, such as a few hours or days. The order ofapplying the compounds of formula I selected from Tables Y-1 to Y-8, X-1to X-8, U-1 to U-2 and V-1 to V-6 and Table P and the active ingredientsas described above is not essential for working the present invention.

The compositions according to the invention can also comprise furthersolid or liquid auxiliaries, such as stabilizers, for exampleunepoxidized or epoxidized vegetable oils (for example epoxidizedcoconut oil, rapeseed oil or soya oil), antifoams, for example siliconeoil, preservatives, viscosity regulators, binders and/or tackifiers,fertilizers or other active ingredients for achieving specific effects,for example bactericides, fungicides, nematocides, plant activators,molluscicides or herbicides.

The compositions according to the invention are prepared in a mannerknown per se, in the absence of auxiliaries for example by grinding,screening and/or compressing a solid active ingredient and in thepresence of at least one auxiliary for example by intimately mixingand/or grinding the active ingredient with the auxiliary (auxiliaries).These processes for the preparation of the compositions and the use ofthe compounds I for the preparation of these compositions are also asubject of the invention.

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is generally 1 to 2000 g of active ingredient per hectare, inparticular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection isapplication to the foliage of the plants (foliar application), it beingpossible to select frequency and rate of application to match the dangerof infestation with the pest in question. Alternatively, the activeingredient can reach the plants via the root system (systemic action),by drenching the locus of the plants with a liquid composition or byincorporating the active ingredient in solid form into the locus of theplants, for example into the soil, for example in the form of granules(soil application). In the case of paddy rice crops, such granules canbe metered into the flooded paddy-field.

The compounds of the invention and compositions thereof are also besuitable for the protection of plant propagation material, for exampleseeds, such as fruit, tubers or kernels, or nursery plants, againstpests of the abovementioned type. The propagation material can betreated with the compound prior to planting, for example seed can betreated prior to sowing. Alternatively, the compound can be applied toseed kernels (coating), either by soaking the kernels in a liquidcomposition or by applying a layer of a solid composition. It is alsopossible to apply the compositions when the propagation material isplanted to the site of application, for example into the seed furrowduring drilling. These treatment methods for plant propagation materialand the plant propagation material thus treated are further subjects ofthe invention. Typical treatment rates would depend on the plant andpest/fungi to be controlled and are generally between 1 to 200 grams per100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds,such as between 10 to 100 grams per 100 kg of seeds.

The term seed embraces seeds and plant propagules of all kinds includingbut not limited to true seeds, seed pieces, suckers, corns, bulbs,fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like andmeans in a preferred embodiment true seeds.

The present invention also comprises seeds coated or treated with orcontaining a compound of formula I. The term “coated or treated withand/or containing” generally signifies that the active ingredient is forthe most part on the surface of the seed at the time of application,although a greater or lesser part of the ingredient may penetrate intothe seed material, depending on the method of application. When the saidseed product is (re)planted, it may absorb the active ingredient. In anembodiment, the present invention makes available a plant propagationmaterial adhered thereto with a compound of formula (I). Further, it ishereby made available, a composition comprising a plant propagationmaterial treated with a compound of formula (I).

Seed treatment comprises all suitable seed treatment techniques known inthe art, such as seed dressing, seed coating, seed dusting, seed soakingand seed pelleting. The seed treatment application of the compoundformula (I) can be carried out by any known methods, such as spraying orby dusting the seeds before sowing or during the sowing/planting of theseeds.

BIOLOGICAL EXAMPLES Example B1: Activity on Bemisia tabaci (Cotton WhiteFly)

Cotton leaf discs were placed on agar in 24-well microtiter plates andsprayed with aqueous test solutions prepared from 10′000 ppm DMSO stocksolutions. After drying the leaf discs were infested with adult whiteflies. The samples were checked for mortality 6 days after incubation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm: P3, P4, P6, P8, P10, P13, P14, and P15.

Example B2: Activity on Diabrotica balteata (Corn Root Worm)

Maize sprouts placed onto an agar layer in 24-well microtiter plateswere treated with aqueous test solutions prepared from 10′000 ppm DMSOstock solutions by spraying. After drying, the plates were infested withL2 larvae (6 to 10 per well). The samples were assessed for mortalityand growth inhibition in comparison to untreated samples 4 days afterinfestation.

The following compounds gave an effect of at least 80% in at least oneof the two categories (mortality or growth inhibition) at an applicationrate of 200 ppm: P3, P4, P5, P7, P8, P10, P11, P12, P13, P14 and P16.

Example B3: Activity on Euschistus heros (Neotropical Brown Stink Bug)

Soybean leaves on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10′000 ppm DMSO stock solutions.After drying the leaves were infested with N2 nymphs. The samples wereassessed for mortality and growth inhibition in comparison to untreatedsamples 5 days after infestation.

The following compounds gave an effect of at least 80% in at least oneof the two categories (mortality or growth inhibition) at an applicationrate of 200 ppm: P3, P4, P8, P9, P10, P13, P14, and P15.

Example B4: Activity on Myzus persicae (Green Peach Aphid)

Sunflower leaf discs were placed onto agar in a 24-well microtiter plateand sprayed with aqueous test solutions prepared from 10′000 ppm DMSOstock solutions. After drying, the leaf discs were infested with anaphid population of mixed ages. The samples were assessed for mortality6 days after infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm: P3, P4, P5, P6, P7, P8, P9, P10, P11, P12,P13, P14, P15, P16, and P17.

Example B5: Activity on Myzus persicae (Green Peach Aphid)

Roots of pea seedlings infested with an aphid population of mixed ageswere placed directly into aqueous test solutions prepared from 10′000DMSO stock solutions. The samples were assessed for mortality 6 daysafter placing seedlings into test solutions.

The following compounds resulted in at least 80% mortality at a testrate of 24 ppm: P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14,P15, P16, and P17.

Example B6: Activity on Plutella xylostella (Diamond Back Moth)

24-well microtiter plates with artificial diet were treated with aqueoustest solutions prepared from 10′000 ppm DMSO stock solutions bypipetting. After drying, the plates were infested with L2 larvae (10 to15 per well). The samples were assessed for mortality and growthinhibition in comparison to untreated samples 5 days after infestation.

The following compounds gave an effect of at least 80% in at least oneof the two categories (mortality or growth inhibition) at an applicationrate of 200 ppm: P3, P4, P5, P6, P7, P8, P11, P12, P14, and P15.

Example B7: Activity on Spodoptera littoralis (Egyptian Cotton LeafWorm)

Cotton leaf discs were placed onto agar in 24-well microtiter plates andsprayed with aqueous test solutions prepared from 10′000 ppm DMSO stocksolutions. After drying the leaf discs were infested with five L1larvae. The samples were assessed for mortality, anti-feeding effect,and growth inhibition in comparison to untreated samples 3 days afterinfestation. Control of Spodoptera littoralis by a test sample is givenwhen at least one of the categories mortality, anti-feedant effect, andgrowth inhibition is higher than the untreated sample.

The following compounds resulted in at least 80% control at anapplication rate of 200 ppm: P3, P4, P5, P7, P8, P11, P12, P14, P15, andP16.

Example B8: Activity on Nilaparvata lugens (Brown Plant Hopper)

Rice plants were treated with the diluted test solutions in a spraychamber. After drying plants were infested with ˜20 N3 nymphs. 7 daysafter the treatment samples were assessed for mortality and growthregulation.

P6, P10, P11, P12, P13, and P15 Example B9: Activity on Nilaparvatalugens (Brown plant hopper) Rice plants cultivated in a nutritivesolution were treated with the diluted test solutions into nourishingcultivation system. 1 day after application plants were infested with˜20 N3 nymphs. 7 days after infestation samples were assessed formortality and growth regulation.

P6, P10, P11, P12, P13, and P15

Example B10: Activity on Tetranychus urticae (Two-Spotted Spider Mite)

Bean leaf discs on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10′000 ppm DMSO stock solutions.After drying the leaf discs were infested with a mite population ofmixed ages. The samples were assessed for mortality on mixed population(mobile stages) 8 days after infestation.

The following compound resulted in at least 80% mortality at anapplication rate of 200 ppm: P3.

Example B11: Activity on Plutella xylostella (Diamond Back Moth)

24-well microtiter plates with artificial diet were treated with aqueoustest solutions prepared from 10′000 ppm DMSO stock solutions bypipetting. After drying, Plutella eggs were pipetted through a plasticstencil onto a gel blotting paper and the plate was closed with it. Thesamples were assessed for mortality and growth inhibition in comparisonto untreated samples 8 days after infestation.

The following compounds gave an effect of at least 80% in at least oneof the two categories (mortality or growth inhibition) at an applicationrate of 200 ppm: P16, P17, P18, and P19.

Example B12: Activity on Heterodera schachtii Juvenile Mobility In VitroProfiling in 96 Well Plate

Test solutions are prepared from 10′000 ppm DMSO stock solutions with aTECAN robot to achieve 20 μL of 500, 100, 50, 25, 12.5 and 6.25 ppm. Foreach concentration three replicates are produced. Per well, 80 μLnematode solution is added containing 100 to 150 freshly harvestedsecond stage juveniles of Heterodera schachtii. The plates are coveredand stored at room temperature in the dark and incubated for 48 h.Mobility of the exposed juveniles in a treated well is measured using animaging tool and compared to an average of 12 untreated replicates.

The following compounds achieved at least 60% control at 100 ppm after48 h: P10, P15.

1. A compound of formula (I)

wherein A is CH or N R₁ is C₁-C₄ alkyl R₂ is hydrogen, cyano, —C(O)R₇,—C(O)OR₈, C₁-C₆alkyl or —CONR₉R₁₀, SO₂R₁₁ wherein R₇ is hydrogen,C₁-C₆alkyl or C₁-C₆haloalkyl and R₅ is C₁-C₆alkyl or C₁-C₆haloalkyl; R₉,R₁₀ independently of one another are hydrogen or C₁-C₆alkyl; R₁₁ isC₁-C₆alkyl; R₃ is hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano, —CO₂H,—CO₂NH₂, C₁-C₄alkoxycarbonyl, C₁-C₄alkylaminocarbonyl,C₁-C₄dialkylaminocarbonyl n is 0 or 1; Q is a radical selected from thegroup consisting of formulae Q₁, Q₂, Q₃, Q₄ and Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein R₄ is halogen, C₁-C₆haloalkyl,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonylor C₁-C₆haloalkoxy; X₁ is O or NR₅; R₅ is C₁-C₄alkyl; R₆ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄alkoxy, or C₃-C₆cycloalkyl; G₁ and G₂ are,independently from each other, N or CH; or an agrochemically acceptablesalt, stereoisomer, enantiomer, tautomer or N-oxide of a compound offormula I.
 2. The compound according to claim 1, wherein: A is CH or N;R₁ is ethyl, propyl or isopropyl; R₂ is hydrogen, cyano, C₁-C₃ alkyl,C₁-C₃alkylcarbonyl, C₁-C₃alkoxycarbonyl, C₁-C₃haloalkylcarbonyl; R₃ ishydrogen, C₁-C₃haloalkyl, cyano, —CO₂H, —CO₂NH₂,C₁-C₄dialkylaminocarbonyl; and n is
 1. 3. The compound according toclaim 1, wherein: A is CH or N; R₁ is ethyl; R₂ is hydrogen; R₃ ishydrogen, C₁-C₂haloalkyl, cyano, —CO₂NH₂, C₁-C₂dialkylaminocarbonyl; andn is
 1. 4. The compound according to claim 1, wherein: A is CH or N; R₁is ethyl; R₂ is hydrogen; R₃ is hydrogen, cyano or CO₂NH₂; and n is 1.5. The compound according to claim 1, wherein: A is CH or N; R₁ isethyl; R₂ is hydrogen; R₃ is hydrogen or cyano; and n is
 1. 6. Thecompound according to claim 1, wherein: Q is a radical selected from Q₁,Q₂, Q₄ and Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein R₄ is C₁-C₂haloalkyl,C₁-C₂haloalkylsulfanyl, C₁-C₂haloalkylsulfinyl orC₁-C₂haloalkylsulfonyl; X₁ is oxygen or NCH₃; R₆ is C₁-C₂alkyl,C₁-C₂haloalkyl, C₁-C₂alkoxy or cyclopropyl; and G₁ and G₂ are,independently from each other, N or CH.
 7. The compound according toclaim 1: is a radical selected from Q₁, Q₂ and Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein R₄ is C₁-C₂fluoroalkyl,trifluoromethylsulfanyl, trifluoromethylsulfinyl,trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl,or difluoromethylsulfonyl; X₁ is NCH₃; R₆ is methyl, ethyl,2,2,2-trifluoroethyl, methoxy or cyclopropyl; and G₁ and G₂ are,independently from each other, N or CH.
 8. The compound according toclaim 1, wherein: Q is a radical selected from Q₁ and Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein R₄ is trifluoromethyl,pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl ortrifluoromethylsulfonyl; X₁ is NCH₃; R₆ is ethyl, methoxy orcyclopropyl; and G₁ is N and G₂ is CH, or G₁ is CH and G₂ is N, or G₁and G₂ are N, or G₁ and G₂ are CH.
 9. The compound according to claim 1,wherein: Q is radical Q₁

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein R₂ is trifluoromethyl; X₁ isNCH₃; and G₁ is N and G₂ is CH, G₁ is CH and G₂ is N, or G₁ and G₂ areN.
 10. The compound according to claim 1, wherein: A is CH or N; R₁ isethyl, propyl or isopropyl; R₂ is hydrogen, cyano, C₁-C₃ alkyl,C₁-C₃alkylcarbonyl, C₁-C₃alkoxycarbonyl, C₁-C₃haloalkylcarbonyl; R₃ ishydrogen, C₁-C₃haloalkyl, cyano, CO₂H, CO₂NH₂,C₁-C₄dialkylaminocarbonyl; n is 1; Q is a radical selected from Q₁, Q₂,Q₄ and Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein R₄ is C₁-C₂haloalkyl,C₁-C₂haloalkylsulfanyl, C₁-C₂haloalkylsulfinyl orC₁-C₂haloalkylsulfonyl; X₁ is oxygen or NCH₃; R₆ is C₁-C₂alkyl,C₁-C₂haloalkyl, C₁-C₂alkoxy or cyclopropyl; and G₁ and G₂ are,independently from each other, N or CH.
 11. The compound according toclaim 1, wherein: A is CH or N; R₁ is ethyl; R₂ is hydrogen; R₃ ishydrogen, C₁-C₂haloalkyl, cyano, CO₂NH₂, C₁-C₂dialkylaminocarbonyl; n is1; Q is a radical selected from Q₁, Q₂ and Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein R₄ is C₁-C₂fluoroalkyl,trifluoromethylsulfanyl, trifluoromethylsulfinyl,trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl,or difluoromethylsulfonyl; X₁ is NCH₃; R₆ is methyl, ethyl,2,2,2-trifluoroethyl, methoxy or cyclopropyl; and G₁ and G₂ are,independently from each other, N or CH.
 12. The compound according toclaim 1, wherein: A is CH or N; R₁ is ethyl; R₂ is hydrogen; R₃ ishydrogen, cyano or CO₂NH₂; n is 1; Q is a radical selected from Q₁ andQ₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein R₄ is trifluoromethyl,pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl ortrifluoromethylsulfonyl; X₁ is NCH₃; R₆ is ethyl, methoxy orcyclopropyl; and G₁ is N and G₂ is CH, or G₁ is CH and G₂ is N, or G₁and G₂ are N, or G₁ and G₂ are CH.
 13. The compound according to claim1, wherein: A is CH or N; R₁ is ethyl; R₂ is hydrogen; R₃ is hydrogen orcyano; n is 1; Q is radical Q₁

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and wherein R₂ is trifluoromethyl; X₁ isNCH₃; and G₁ is N and G₂ is CH, G₁ is CH and G₂ is N, or G₁ and G₂ areN.
 14. The compound according to claim 1, wherein: Q is a radicalselected from Q₁₋₁, Q₁₋₂, Q₁₋₃, Q₁₋₄ and Q₁₋₅; preferably Q is a radicalselected from Q₁₋₂, Q₁₋₃, Q₁₋₄ and Q₁₋₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; and R₄ is trifluoromethyl,trifluoromethylsulfanyl or trifluoromethylsulfonyl.
 15. The compoundaccording to claim 1, wherein: Q is a radical selected from Q₅

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; R₄ is trifluoromethyl,trifluoromethylsulfanyl or trifluoromethylsulfonyl; and R₆ is OCH₃,CH₂CH₃ or cyclopropyl.
 16. The compound according to claim 1, wherein: Qis a radical selected from Q₄

wherein the arrow denotes the point of attachment to the ringincorporating the radical A; R₄ is trifluoromethyl,trifluoromethylsulfanyl or trifluoromethylsulfonyl; and G₁ is N and G₂is CH, G₁ is CH and G₂ is N, G₁ and G₂ are CH, or G₁ and G₂ are N;preferably G₁ is CH and G₂ is N.
 17. A selected from the groupconsisting of:1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarboxamide;1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarboxamide;[5-cyclopropyl-2-[3-methyl-6-(trifluoromethylsulfonyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane;[5-cyclopropyl-2-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane;[5-cyclopropyl-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane;1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile;[5-cyclopropyl-2-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane;1-[5-(ethylsulfonimidoyl)-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile(compound P8);1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile;1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile;[5-cyclopropyl-2-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane;[5-cyclopropyl-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane;1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile;1-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]cyclopropanecarbonitrile;1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile;[5-cyclopropyl-2-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane;1-[5-(ethylsulfonimidoyl)-6-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile;[5-cyclopropyl-2-[5-(trifluoromethylsulfanyl)-1,3-benzoxazol-2-yl]-3-pyridyl]-ethyl-imino-oxo-X⁶-sulfane;and[5-cyclopropyl-2-[5-(trifluoromethylsulfonyl)-1,3-benzoxazol-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ⁶-sulfane.18. A composition comprising an insecticidally, acaricidally,nematicidally or molluscicidally effective amount of a compound offormula (I), or an agrochemically acceptable salt, stereoisomer,enantiomer, tautomer or N-oxide thereof, as defined in claim 1 and,optionally, an auxiliary or diluent.
 19. A method of combating andcontrolling insects, acarines, nematodes or molluscs which comprisesapplying to a pest, to a locus of a pest, or to a plant susceptible toattack by a pest an insecticidally, acaricidally, nematicidally ormolluscicidally effective amount of a compound of formula (I), or anagrochemically acceptable salt, stereoisomer, enantiomer, tautomer orN-oxide thereof, as defined in claim
 1. 20. A method for the protectionof plant propagation material from the attack by insects, acarines,nematodes or molluscs, which comprises treating the propagation materialor the site, where the propagation material is planted, with a compoundaccording to claim 17.